Compositions for dyeing keratin fibers

ABSTRACT

Star polymers comprising (1) a structural fragment acting as a center, and (2) at least three groups radially bound to this center, wherein these groups (i) each have at least one polyether structural unit comprising a polyoxyalkylene chain consisting of either ethylene oxide units or both ethylene oxide and propylene oxide units, wherein the polyoxyalkylene chain has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of the polyoxyalkylene chain, and (ii) each have at least one residue comprising: (a) at least one *—Si(OR) x (R′) 3-x  group, in which R and R′, independently of one another, denote a (C 1  to C 4 ) alkyl group, x denotes 1, 2 or 3; (b) at least one anionic group; (c) at least one quaternized nitrogen atom; or (d) combinations thereof; are suitable for improving synthetic colorings of coloring compounds on keratin-containing fibers.

RELATED DOCUMENTS

The present application claims the benefit and is a U.S. continuation patent application under 35 U.S.C. 111(a) and claims the right of priority under 35 U.S.C. 365 to international patent Application No. PCT/EP2012/072457, filed Nov. 13, 2012, entitled “Compositions for Dyeing Keratin Fibers” which claims benefit of German application No.: 102011089063.7, filed Dec. 19, 2011, these applications are herein incorporated by reference in their entirety.

FIELD OF THE INVENTION

The present specification relates generally to cosmetic agents for coloring keratin-containing fibers. More specifically, the present application relates to a cosmetic agent including a star polymer to improve synthetic colorings of keratin-containing fibers.

BACKGROUND OF THE INVENTION

Various systems provide cosmetic agents for coloring, in particular for keratin-containing fibers, such as human hair. The selection of such a system depends on the requirements of the coloring process.

Oxidation coloring agents are used for permanent, intense colors with corresponding fastness properties. Such coloring agents may conventionally include oxidation dye precursors known as “developer components” and “coupler components.” Under the influence of oxidizing agents, or of atmospheric oxygen the developer components form the actual dyes with one another or by coupling with one or more coupler components. Oxidation coloring agents are characterized by outstanding, long-lasting coloring results. In order to achieve natural-looking colors, however, a mixture of a relatively large number of oxidation dye precursors usually has to be used; in many cases substantive dyes are also used for shading.

Primary aromatic amines having a further free or substituted hydroxyl or amino group in para- or ortho-position, heterocyclic hydrazones, diaminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof may be used as developer components. m-Phenylenediamine derivatives, naphthols, pyridine derivatives, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols may be used as coupler components.

For temporary colors, coloring or tinting agents may be used; these agents include substantive dyes as the coloring component. Substantive dyes are dye molecules which attach directly to the substrate and require no oxidative process to develop the color. These colors are may be significantly more sensitive to shampooing than oxidative colors, such that an often undesired shift in shade, or a visible homogeneous color loss, occurs much more quickly.

Finally, another coloring method has attracted great attention. In this method precursors of the natural hair dye melanin are applied to the substrate, for example hair. Through oxidative processes these melanin precursors then develop nature-analogous dyes in the hair. It is possible to restore the natural hair color of people with gray hair with repeated use in particular of agents including 5,6-dihydroxyindoline. Pigment removal may be carried out using atmospheric oxygen as the sole oxidizing agent, avoiding the need to use a further oxidizing agent. For people whose original hair color is medium blond to brown, indoline may be used as the sole dye precursor. By contrast, for people whose original hair color is red and in particular darker to black, satisfactory results may frequently only be obtained with the additional use of further dye components, in particular special oxidation dye precursors.

One consequence of an improvement in color intensity or coloring power for example of the dyes used is that expensive dyes may be used more economically. The colors obtained should moreover have a high degree of color fastness, with respect to sweat, washing, light or friction for example. Additionally, in the context of hair care in particular, products should be compatible with the use of other hair treatment agents. A uniform color along the keratin-containing fibers is likewise a requirement of a commercially successful coloring agent for keratin-containing fibers. As natural products, keratinic fibers, such as human hair, have uneven structural properties along the fiber. For example, the keratin-containing material of the fiber at the tip and along the length of the hair has been exposed to environmental influences for a longer time than the regions of the fiber in the vicinity of the hair root and therefore exhibits greater changes to the original natural fiber structure. Differences in the fiber structure often lead to an uneven color uptake and to an uneven fading of the color due to environmental influences. The color is visually perceived as uneven.

Consequently, an object of the present specification is therefore to provide a cosmetic composition for coloring keratin-containing fibers which brings about an improved color and does not present the above disadvantages.

Document WO-A1-2009/024450 describes star-shaped polyether-containing compounds which may be used in agents for cleaning surfaces and which inhibit resoiling of the cleaned substrate.

Documents WO-A1-2011/015512, WO-A1-2011/015513 and WO-A1-2011/015514 propose alkoxysilylated, polyether-containing compounds for use on the hair.

Improving the color fastness of synthetic colorings on keratin-containing fibers with alkoxysilylated, polyether-containing compounds is not known in the industry.

Furthermore, other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description of the invention and the appended claims, taken in conjunction with this background of the invention.

BRIEF SUMMARY OF THE INVENTION

A first subject matter of the present specification is therefore the a method to improve synthetic colorings of coloring compounds on keratin-containing fibers. The method includes applying an active agent including star polymers comprising a structural fragment acting as a center and at least three groups radially bound to this center, wherein these groups

-   (i) each have at least one polyether structural unit comprising a     polyoxyalkylene chain consisting of either ethylene oxide units or     both ethylene oxide and propylene oxide units, wherein the     polyoxyalkylene chain has a maximum proportion of 50 weight percent     (wt. %) of propylene oxide units, relative to the weight of the     polyoxyalkylene chain, and -   (ii) each have at least one residue comprising:     -   at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′,         independently of one another, denote a (C₁ to C₄) alkyl group, x         denotes 1, 2 or 3;     -   at least one anionic group;     -   at least one quaternized nitrogen atom; or     -   combinations thereof.

The present specification also provides a cosmetic agent for coloring keratin-containing fibers. The cosmetic agent includes, in a cosmetic carrier, (A) at least one coloring compound, and (B) at least one star polymer including a structural fragment acting as a center, and at least three groups radially bound to this center, wherein the groups (i) each have at least one polyether structural unit comprising a polyoxyalkylene chain consisting of either ethylene oxide units or both ethylene oxide and propylene oxide units, wherein the polyoxyalkylene chain has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of the polyoxyalkylene chain, and (ii) each have at least one residue comprising: (a) at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′, independently of one another, denote a (C₁ to C₄) alkyl group, x denotes 1, 2 or 3; (b) at least one anionic group; (c) at least one quaternized nitrogen atom; or (d) combinations thereof.

The present specification also provides a cosmetic method for treating keratin-including fibers that have been synthetically colored with at least one coloring compound. The method includes applying an agent including at least one star polymer comprising a structural fragment acting as a center, and at least three groups radially bound to this center, wherein the groups (i) each have at least one polyether structural unit comprising a polyoxyalkylene chain consisting of either ethylene oxide units or both ethylene oxide and propylene oxide units, wherein the polyoxyalkylene chain has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of the polyoxyalkylene chain, and (ii) each have at least one residue comprising: (a) at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′, independently of one another, denote a (C₁ to C₄) alkyl group, x denotes 1, 2 or 3; (b) at least one anionic group; (c) at least one quaternized nitrogen atom; or (d) combinations thereof. The method further includes allowing the cosmetic agent to act on keratin-containing fibers that have been synthetically colored with at least one coloring compound, and after a contact time, rinsing the agent from the keratin-containing fibers.

DETAILED DESCRIPTION

The following detailed description of the invention is merely exemplary in nature and is not intended to limit the invention or the application and uses of the invention. Furthermore, there is no intention to be bound by any theory presented in the preceding background of the invention or in the following detailed description of the invention.

The use of an active agent including star polymers during the coloring of keratin-containing fibers improves the color fastness of the color, in particular the wash fastness of the color. Repeated washing of the fibers does not cause uneven coloring along the keratinic fiber from the root to the tips as a result of the color washing out unevenly. The color maintains good equalization.

According to the present specification, the term “keratin-containing fibers,” “keratin fibers,” or similar terminology is understood to mean fur, wool, feathers and in particular human hair.

The coloring compounds within the meaning of the present specification are preferably selected from:

-   (1) at least one oxidation dye precursor of the developer component     type and optionally additionally at least one coupler component -   and/or -   (2) at least one substantive dye -   and/or -   (3) at least one precursor of nature-analogous dyes.

Particularly preferred coloring compounds are selected from at least one oxidation dye precursor of the developer component type and optionally additionally at least one coupler component.

Preferred representatives of the coloring compounds from (1), (2) and (3) (see above) are defined in the second subject matter of the present specification (see below).

Preferred representatives of components (a) and (b) of said active agent combination (see above) are defined in the second subject matter of the present specification (see below).

The cosmetic use of the agent according to the present specification is improved by incorporating said at least one star polymer into a cosmetic carrier. The cosmetic agents for coloring keratin-containing fibers of the second subject matter of the present specification, as specified below, are therefore preferably used.

The present specification therefore secondly provides a cosmetic agent for coloring keratin-containing fibers, in particular human hair, including in a cosmetic carrier

-   (a) at least one star polymer comprising a structural fragment     acting as a center and at least three groups radially bound to this     center, wherein these groups     -   (i) each have at least one polyether structural unit comprising         a polyoxyalkylene chain consisting of either ethylene oxide         units or both ethylene oxide and propylene oxide units, wherein         the polyoxyalkylene chain has a maximum proportion of 50 weight         percent (wt. %) of propylene oxide units, relative to the weight         of the polyoxyalkylene chain, and     -   (ii) each have at least one residue, comprising:         -   at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and             R′, independently of one another, denote a (C₁ to C₄) alkyl             group (preferably methyl or ethyl), x denotes 1, 2 or 3;         -   at least one anionic group;         -   at least one quaternized nitrogen atom; or         -   combinations thereof; -   and -   (b) at least one coloring compound.

In the context of the present specification, if a chemical bond in a structural formula is marked with the symbol *, it denotes a free valence of the corresponding structural fragment.

Polymers are understood according to the present specification to be chemical compounds having a molecular weight of at least 5000 grams per mole (g/mol). Polymers are synthesized from a large number of molecules, in which one type or a plurality of types of atoms or atom groupings (known as constitutive units, basic building blocks, monomers or repeat units) are arranged next to one another in repeating series. Polymers are obtained by a polymerization reaction, which may take place artificially (i.e. synthetically) or naturally.

“Polyether structural unit” is understood to be a chemical structural fragment including a polyoxyalkylene chain consisting of either ethylene oxide units or both ethylene oxide and propylene oxide units, wherein the polyoxyalkylene chain has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of the polyoxyalkylene chain. The polyether structural unit is optionally covalently bound to said structural fragment acting as a center either directly or optionally through a chemical bond with a mediating structural fragment. Organic compounds or inorganic metal oxides preferably serve as skeletal molecules in this case. The first group forms a polyether-modified organic compound including the polyether structural unit(s). The second group forms a polyether-modified solid particle including the polyether structural unit(s).

“Organic compounds” are understood to be chemical compounds based on a hydrocarbon structural fragment. Corresponding hydrocarbon structural fragments are derived from linear, branched, cyclic or heterocyclic hydrocarbons, all of which may each be saturated, unsaturated or aromatic.

“Polyether-modified organic compounds” are understood according to the present specification to be organic compounds that are modified with at least one polyether structural unit, the polyether structural unit in each case forming a chemical bond with the organic compound to be modified.

“Solid particle” is understood to mean any solid that is in particulate form at room temperature.

“Polyether-modified solid particles” are understood according to the present specification to be solid particles which are surface-modified with polyethers, wherein the polyethers include a polyoxyalkylene chain consisting of either ethylene oxide units or both ethylene oxide and propylene oxide units, wherein the polyoxyalkylene chain has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of the polyoxyalkylene chain.

Within the meaning of the present specification an ethylene oxide unit is understood to be a unit of general formula (1) *—CH₂—CH₂—O—*  Formula (1) and within the meaning of the present specification a propylene oxide unit is understood to be a unit of general formula (2) *—CH₂—CH(CH₃)—O—*  Formula (2)

If the polyoxyalkylene chain of the polyether structural unit includes ethylene oxide and propylene oxide units, the maximum proportion of propylene oxide units in the polyether structural unit according to the present specification of said star polymers is preferably less than or equal to 50 wt. %, more preferably less than or equal to 40 wt. % and particularly preferably at most 30 wt. %, relative to the weight of the polyoxyalkylene chain.

Star polymers which are preferred according to the present specification preferably have at least three residues radially bound to the center, each having the structural unit *—K′-A-K-T, in which

-   A denotes a polyoxyalkylene chain consisting of either ethylene     oxide units or both ethylene oxide and propylene oxide units,     wherein the polyoxyalkylene chain has a maximum proportion of 50 wt.     % of propylene oxide units, relative to the weight of A, -   K and K′ independently of one another, denote a connectivity     selected from a covalent bond or from a molecular fragment having     two free valences, -   T denotes a structural fragment comprising     -   at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′,         independently of one another, denote a (C₁ to C₄) alkyl group         (preferably methyl or ethyl), x denotes 1, 2 or 3, or     -   at least one anionic group, or     -   at least one quaternized nitrogen atom.

It is especially preferable for A to denote a structural fragment of formula (A1) *—(OCH₂CH₂)_(n)—(OCH₂CH(CH₃))_(m)—*  (A1) in which n denotes an integer from 1 to 500, m denotes an integer from 0 to 500, and n and m are selected such that the structural fragment of formula (A1) has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of the structural fragment (A1). The ethylene oxide and propylene oxide units according to formula (PE-1) or according to formula (A1) may be randomly distributed or distributed as a gradient or may be present in at least two blocks.

Preferred residues *—K′-A-K-T are those in which the residues K and K′, independently of one another, denote a covalent bond, an oxy group, an imino group, a (C₁ to C₆) alkylene group or at least one of the following connectivities (K1) to (K10)

in which

-   R and R″ independently of one another, denote methylene,     ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl,     butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl or phenylene, -   R′ denotes a hydrogen atom or a (C₁ to C₄) alkyl group, -   R′″ independently of one another, denotes a (C₁ to C₄) alkyl group     or an aryl group.

The “T” in the residue *—K′-A-K-T particularly preferably denotes a structural fragment comprising

-   -   at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′,         independently of one another, denote a (C₁ to C₄) alkyl group         (in particular methyl or ethyl), x denotes 1, 2 or 3,         or     -   at least one anionic group.

Said *—Si(OR)_(x)(R′)_(3-x) group is a most particularly preferred group of the structural fragment T.

Preferred cosmetic carriers are aqueous cosmetic carriers, alcoholic cosmetic carriers or aqueous-alcoholic cosmetic carriers. For the purposes of coloring keratin-containing fibers such carriers are for example lotions, water-in-oil emulsions, oil-in-water emulsions, creams, gels, foams or other preparations that are suitable for use on the hair.

Within the meaning of the present specification, aqueous-alcoholic carriers are understood to be aqueous compositions including 3 to 70 weight percent (wt. %) of an organic solvent, in particular a C₁-C₇ alcohol (preferably ethanol, isopropanol, glycerol, benzyl alcohol, ethyl diglycol, 1,2-propylene glycol or 1,3-propylene glycol, methoxybutanol). All water-soluble organic solvents are preferred here.

Said star polymers are preferably included in the agents according to the present specification in an amount from 0.01 to 15.0 wt. %, particularly preferably from 0.1 to 8.0 wt. %, most particularly preferably from 0.2 to 5.0 wt. %, most preferably from 0.25 to 2.5 wt. %, relative in each case to the total weight of the agent.

It is likewise preferable according to the present specification for said star polymers of component (a) and the coloring compounds of component (b) to be used in the agents according to the present specification in a weight ratio range from 10 to 1 to 1 to 15, preferably from 3 to 1 to 1 to 10, particularly preferably from 1 to 1 to 1 to 8.

Cosmetic agents which are preferred according to the present specification include at least one star polymer compound of general formula (PE-1) [Q

K′-A-K-T)_(n)  (PE-1) in which

-   A denotes a polyoxyalkylene chain consisting of either ethylene     oxide units or both ethylene oxide and propylene oxide units,     wherein the polyoxyalkylene chain has a maximum proportion of 50 wt.     % of propylene oxide units, relative to the weight of A, -   K and K′ independently of one another, denote a connectivity     selected from a covalent bond or a molecular fragment having two     free valences, -   T denotes a structural fragment comprising:     -   at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′,         independently of one another, denote a (C₁ to C₄) alkyl group         (in particular methyl or ethyl), x denotes 1, 2 or 3;     -   at least one anionic group;     -   at least one quaternized nitrogen atom; or     -   combinations thereof, -   Q denotes an organic structural fragment acting as a center and     derived from linear, branched, cyclic or heterocyclic hydrocarbons,     all of which may each be saturated, unsaturated or aromatic, -   n denotes an integer from 3 to 64 (in particular 3, 4, 5, 6, 7 or     8).

The “A” according to formula (PE-1) preferably denotes a structural fragment of formula (A1) *—(OCH₂CH₂)_(p)—(OCH₂CH(CH₃))_(m)—*  (A1) in which

-   -   p denotes an integer from 1 to 500,     -   m denotes an integer from 0 to 500, and         p and m are selected such that the structural fragment of         formula (A1) has a maximum proportion of 50 wt. % of propylene         oxide units, relative to the weight of the structural fragment         (A1). The ethylene oxide and propylene oxide units according to         formula (PE-1) or according to formula (A1) may be randomly         distributed or distributed as a gradient or may be present in at         least two blocks.

If group “A” of the compounds according to formula (PE-1) (or according to all subsequent formulae including group A) denotes a polyoxyalkylene chain consisting of both ethylene oxide and propylene oxide units, the maximum proportion of propylene oxide units is preferably less than or equal to 50 wt. %, more preferably less than or equal to 40 wt. % and particularly preferably at most 30 wt. %, relative to the weight of A.

The residues K and K′ according to formula (PE-1) preferably (and independently of one another) denote a covalent bond, an oxy group, a (C₁ to C₆) alkylene group, an imino group or at least one of the following connectivities (K1) to (K10)

in which

-   R and R″ independently of one another, denote methylene,     ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl,     butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl or phenylene, -   R′ denotes a hydrogen atom or a (C₁ to C₄) alkyl group, -   R′″ independently of one another, denotes a (C₁ to C₄) alkyl group     or an aryl group.

The “T” according to formula (PE-1) preferably denotes a *—Si(OR)_(x)(R′)_(3-x) residue, in which R and R′, independently of one another, denote a (C₁ to C₄) alkyl group (preferably methyl or ethyl) and x denotes 2 or 3 (preferably “T” denotes a triethoxysilyl radical).

The structural fragment —K-T according to formula (PE-1) most particularly preferably denotes a group

The residue Q of formula (PE-1) preferably denotes an organic structural fragment having 2 to 30 carbon atoms, particularly preferably having 2 to 20 carbon atoms.)

Q is preferably derived from glycerol, a monosaccharide, or a disaccharide. Q is most particularly preferably derived from a compound selected from sorbitol, 1,5-anhydrosorbitol, 1,4-anhydrosorbitol, inositol, xylitol, mannitol, gluconolactone, glucuronic acid, 1,2,6-hexanetriol, hydroxyethyl sorbitol, phytantriol, hydroxypropyl phytantriol, lactitol, maltitol, pentaerythritol, polyglycerol-3, glucose, fructose, galactose, ribose, xylose, mannose, sucrose, cellobiose, gentiobiose, isomaltose, lactose, lactulose, maltose, maltulose, melibiose, trehalose, nigerose, palatinose, rutinose, and arabinose.

Most particularly preferred star polymers are selected from at least one compound of formula (PE-1a), (PE-1b), (PE-1c), (PE-1d), (PE-1e), (PE-1f) or mixtures thereof,

in which at least three R groups denote a *—(CH₂CH₂O)_(p)—(CHCH₃CH₂O)_(m)—K-T group and the other R groups denote a hydrogen atom or a *—K-T group, in which, independently of one another,

-   -   p denotes an integer from 1 to 500 and m an integer from 0 to         500 and p and m have a ratio to one another such that there is a         maximum proportion of 50 wt. % (preferably a maximum of 40 wt.         %, particularly preferably a maximum of 30 wt. %) of propylene         oxide units, relative to the weight of the corresponding         polyoxyalkylene chain,     -   K denotes a connectivity selected from a covalent bond or from a         molecular fragment having two free valences,     -   T denotes a molecular fragment comprising at least one         *—Si(OR)_(x)(R′)_(3-x) residue, in which R and R′, independently         of one another, denote a (C₁ to C₄) alkyl group (preferably         methyl or ethyl), and x denotes 1, 2 or 3;

in which at least three R groups denote a *—(CH₂CH₂O)_(p)—(CHCH₃CH₂O)_(m)—K-T group and the other R groups denote a hydrogen atom or a *—K-T group, in which, independently of one another,

-   -   p denotes an integer from 1 to 500 and m an integer from 0 to         500 and p and m have a ratio to one another such that there is a         maximum proportion of 50 wt. % (preferably a maximum of 40 wt.         %, particularly preferably a maximum of 30 wt. %) of propylene         oxide units, relative to the weight of the corresponding         polyoxyalkylene chain,     -   K denotes a connectivity selected from a covalent bond or from a         molecular fragment having two free valences,     -   T denotes a molecular fragment comprising at least one         *—Si(OR)_(x)(R′)_(3-x) residue, in which R and R′, independently         of one another, denote a (C₁ to C₄) alkyl group (preferably         methyl or ethyl), and x denotes 1, 2 or 3;

in which at least three R groups denote a *—(CH₂CH₂O)_(p)—(CHCH₃CH₂O)_(m)—K-T group and the other R groups denote a hydrogen atom or a *—K-T group, in which, independently of one another,

-   -   p denotes an integer from 1 to 500 and m an integer from 0 to         500 and p and m have a ratio to one another such that there is a         maximum proportion of 50 wt. % (preferably a maximum of 40 wt.         %, particularly preferably a maximum of 30 wt. %) of propylene         oxide units, relative to the weight of the corresponding         polyoxyalkylene chain,     -   K denotes a connectivity selected from a covalent bond or from a         molecular fragment having two free valences,     -   T denotes a molecular fragment comprising at least one         *—Si(OR)_(x)(R′)_(3-x) residue, in which R and R′, independently         of one another, denote a (C₁ to C₄) alkyl group (preferably         methyl or ethyl), and x denotes 1, 2 or 3;

in which at least three R groups denote a —(CH₂CH₂O)_(p)—(CHCH₃CH₂O)_(m)—K-T group and the other R groups denote a hydrogen atom or a —K-T group, in which, independently of one another,

-   -   p denotes an integer from 1 to 500 and m an integer from 0 to         500 and p and m have a ratio to one another such that there is a         maximum proportion of 50 wt. % (preferably a maximum of 40 wt.         %, particularly preferably a maximum of 30 wt. %) of propylene         oxide units, relative to the weight of the corresponding         polyoxyalkylene chain,     -   K denotes a connectivity selected from a covalent bond or from a         molecular fragment having two free valences,     -   T denotes a molecular fragment comprising at least one         *—Si(OR)_(x)(R′)_(3-x) residue, in which R and R′, independently         of one another, denote a (C₁ to C₄) alkyl group (preferably         methyl or ethyl), and x denotes 1, 2 or 3;

in which, independently of one another,

-   -   p denotes an integer from 1 to 500 and m an integer from 0 to         500 and p and m have a ratio to one another such that there is a         maximum proportion of 50 wt. % (preferably a maximum of 40 wt.         %, particularly preferably a maximum of 30 wt. %) of propylene         oxide units, relative to the weight of the corresponding         polyoxyalkylene chain,     -   K independently of one another, denotes a connectivity selected         from a covalent bond or from a molecular fragment having two         free valences,     -   T independently of one another, denotes a molecular fragment         comprising at least one *—Si(OR)_(x)(R′)_(3-x) residue, in which         R and R′, independently of one another, r denote a (C₁ to C₄)         alkyl group (preferably methyl or ethyl), and x denotes 1, 2 or         3.

The ethylene oxide and propylene oxide units may be randomly distributed, distributed as a gradient or may be present in at least two blocks.

The previously preferred groups K and T apply to formulae (PE-1a) to (PE-1f). The structural fragment —K-T according to formulae (PE-1a) to (PE-1f) most particularly preferably denotes a group

The star polymers of formula (PE-1) are preferably included in the agents according to the present specification in an amount from 0.01 to 15.0 wt. %, particularly preferably from 0.1 to 8.0 wt. %, most particularly preferably 0.2 to 5.0 wt. %, most preferably from 0.25 to 2.5 wt. %, relative in each case to the weight of the total agent.

Preferred cosmetic agents according to the present specification include, in a cosmetically acceptable carrier,

-   (a) star polymers which are obtained by reacting     -   (i) organic compounds including at least three residues selected         from a hydroxyl group and/or an amino group (preferred according         to the present specification are a hydroxyl group, a primary         amino group, a secondary amino group; hydroxyl groups are         particularly preferred) with     -   (ii) at least 3 molar equivalents of at least one polyether of         formula (I)         T-K′-A-K′—Y  (I)         -   in which         -   A denotes a polyoxyalkylene chain consisting of either             ethylene oxide units or both ethylene oxide and propylene             oxide units, wherein the polyoxyalkylene chain has a maximum             proportion of 50 wt. % of propylene oxide units, relative to             the weight of A,         -   K and K′ independently of one another, denote a connectivity             selected from a covalent bond or from a molecular fragment             having two free valences,         -   T denotes at least one of the following:             -   a *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′,                 independently of one another, denote a (C₁ to C₄) alkyl                 group (in particular methyl or ethyl), x denotes 1, 2 or                 3, or             -   an anionic group, or             -   a quaternized nitrogen atom, or             -   combinations thereof,         -   Y denotes a group that is reactive to hydroxyl groups and/or             amino groups, -   and -   (b) at least one coloring compound.

The specified molar equivalents relate to the amount of substance in the organic compound that was used.

The organic compound having at least three said residues (cf. (a)(i)) is preferably selected from glycerol, a monosaccharide, or a disaccharide. Said organic compound is particularly preferably selected from sorbitol, 1,5-anhydrosorbitol, 1,4-anhydrosorbitol, inositol, xylitol, mannitol, gluconolactone, glucuronic acid, 1,2,6-hexanetriol, hydroxyethyl sorbitol, phytantriol, hydroxypropyl phytantriol, lactitol, maltitol, pentaerythritol, polyglycerol-3, glucose, fructose, galactose, ribose, xylose, mannose, sucrose, cellobiose, gentiobiose, isomaltose, lactose, lactulose, maltose, maltulose, melibiose, trehalose, nigerose, palatinose, rutinose, and arabinose.

For the residues A, K, K′ and T the preferred examples listed under formula (PE-1) apply.

The residue Y according to formula (I) preferably denotes

-   -   an isocyanate functional group (the isocyanate functional group         is particularly preferred)     -   a *—Si(OR)_(x)(R′)_(3-x) group     -   in which R and R′, independently of one another, denote a (C₁ to         C₄) alkyl group (preferably methyl or ethyl) and x denotes 1, 2         or 3,     -   a *—Si(R)_(x)(R′)_(3-x) group     -   in which R denotes a halogen atom (preferably chlorine or         bromine) and R′, independently of one another, denotes a (C₁ to         C₄) alkyl group (preferably methyl or ethyl) and x denotes 1, 2         or 3,     -   a T-K—C(O)—O—C(O)—* group, in which T and K are as defined         according to formula (I),     -   a *—C(O)—Hal group, wherein Hal denotes chlorine or bromine,     -   an epoxy group,     -   a formyl group.

The star polymers of this example are preferably included in the agents according to the present specification in an amount from 0.01 to 10.0 wt. %, particularly preferably from 0.1 to 2.0 wt. %, most particularly preferably 0.2 to 1.0 wt. %, relative in each case to the total weight of the agent.

The polyethers of formula (I) preferably have a molar mass from 1 to 200 kiloDaltons (kDa), particularly preferably from 1 to 10 kDa.

The polyethers of formula (I) for use within the context of the present specification for producing the star polymers may be obtained by reacting at least one compound of formula (II): X-A-X′  (II) in which

-   A denotes a polyoxyalkylene chain consisting of either ethylene     oxide units or both ethylene oxide and propylene oxide units,     wherein the polyoxyalkylene chain has a maximum proportion of 50 wt.     % of propylene oxide units, relative to the weight of A, -   X and X′ independently of one another, denote a structural fragment     including an OH, NH₂ or NHR group     with at least 2 molar equivalents of one or more compounds of     formula (III)     Y—K-T  (III)     in which -   Y denotes an —OH—, —NH₂—, NHR—, NR₂-reactive group, -   K denotes a connectivity selected from a covalent bond or from a     molecular fragment having two free valences, -   T denotes a molecular fragment comprising at least one of the     following:     -   a *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′, independently         of one another, denote a (C₁ to C₄) alkyl group (preferably         methyl or ethyl), x denotes 1, 2 or 3, or     -   an anionic group, or     -   a quaternized nitrogen atom.

The specified molar equivalents relate to the amount of organic compound(s) of formula (II) that are used.

According to the above manufacturing method for producing the compounds of formula (I), exemplary compounds of formula (II) include dihydroxy-terminated polyoxyalkylene diols, diamino-terminated polyoxyalkylene diamines, monohydroxy-monoamine-terminated polyoxyalkylene-monol monoamines, monohydroxy-monoalkoxy-terminated polyoxyalkylene monols or monoamino-monoalkoxy-terminated polyoxyalkylene monoamines. The diamines and diols being preferred.

The residues X and X′ of formula (II) preferably (and independently of one another) denote OH, NH₂ and NHR, particularly preferably OH and NH₂.

The residue R in the NHR and NR₂ groups of formula (III) preferably denotes a linear or branched alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms.

The average molecular weight of the compound of formula (II) is preferably 500 to 30,000 g/mol, particularly preferably 1000 to 20,000, better still 2000 to 18,000 g/mol, and may be determined by end-group analysis, for example.

For the residues A, K, K′ and T the preferred examples listed under formula (PE-1) apply.

Within the context of a preferred example for the production of the star polymers according to the present specification, at least one molecular fragment T of formula (PE-1) or formula (I) or formula (III) includes at least one anionic group.

According to the present specification the molecular fragments T of formula (I) or formula (III) which have at least one anionic group are preferably a molecular fragment including from 1 to 5, preferably 3, 4 or 5, deprotonatable acid groups. The anionic groups or the deprotonatable acid groups of said molecular fragments T of formula (I) or formula (III) are preferably selected from a carboxyl group and/or a sulfonic acid group and/or a phosphate or the salt forms thereof (preferably a carboxyl group and/or a sulfonic acid group or the salt forms thereof, particularly preferably a carboxyl group or the salt form thereof).

In a particularly preferred example the molecular fragment T of formula (I) or formula (III) includes at least one, preferably at least two, particularly preferably 1 to 5, above all 2 to 5, in particular 2, 3, 4 or 5 carboxymethyl units. In a most particularly preferred example said molecular fragment is an ethylenediamine triacetate unit that is covalently bound to the connectivity K of formula (I) or formula (III) via one of its nitrogen atoms.

In a preferred example according to the present specification for producing the star polymers according to the present specification the molecular fragment T of formula (PE-1) or formula (I) or formula (III) is a silyl group of general formula (IV) *—CR^(a) ₂—Si(OR^(b))_(r)(R^(c))_(3-r)  (IV), in which

-   R^(a) denotes hydrogen or C₁₋₆ alkyl, -   R^(b) denotes —Si(R^(d))_(t)(R^(e))_(3-t), -   R^(c) denotes (C₁ to C₆) alkyl, (C₁ to C₆) alkoxy or hydroxy,     preferably (C₁ to C₆) alkoxy or hydroxy, -   R^(d) denotes a negatively charged group, -   R^(e) denotes (C₁ to C₆) alkyl, C₁₋₆ alkoxy or hydroxy, preferably     (C₁ to C₆) alkoxy or hydroxy, -   r denotes a number from 1 to 3, preferably 1, -   t denotes a number from 1 to 3, preferably 1.

R^(d) preferably denotes a unit including 1 to 5, preferably 3, 4 or 5 acid groups, in particular carboxylic acid groups.

R^(d) of formula (IV) particularly preferably denotes a group *—B—[(N(CH₂COOM)-B′)_(y)—N(CH₂COOM)₂] in which

-   B denotes a (C₁ to C₆) alkylene residue (preferably ethane-1,2-diyl,     propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl,     butane-1,3-diyl, butane-1,4-diyl), -   B′ denotes a (C₁ to C₆) alkylene residue (preferably     ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl,     butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl), -   M independently of one another, denotes a hydrogen atom or an     equivalent of a monovalent or polyvalent cation, -   y denotes 1 or 2 (preferably 1).

If the above group is present in acid form, the residue M denotes a hydrogen atom. In that case, the —COOH fragments form a carboxyl group. If the above group is present in salt form (carboxylate), M denotes an equivalent of a monovalent or polyvalent cation. For reasons of electroneutrality the mono- or polyvalent cation M^(z+) having a charge number z of one or more serves only to compensate for the simple negative charge of the carboxylate that is present during salt formation. The equivalent of the corresponding cation which is to be used for this purpose is 1/z. In the case of salt formation the fragment —COOM denotes the group: —COO⁻1/z(M^(z+))

In principle, all physiologically acceptable cations are suitable as mono- or polyvalent cations M^(z+). In particular these are metal cations of the physiologically acceptable metals from groups Ia, Ib, IIa, IIb, IIIb, VIa or VIII of the periodic table, ammonium ions, as well as cationic organic compounds having a quaternized nitrogen atom. Cationic organic compounds having a quaternized nitrogen atom are formed, for example, by protonation of primary, secondary or tertiary organic amines with an acid, such as for example with compounds of the above group R^(d) in its acid form, or by permanent quaternization of said organic amines. Examples of these cationic organic ammonium compounds are 2-ammonioethanol and 2-trimethyl ammonioethanol. M preferably denotes a hydrogen atom, an ammonium ion, an alkali metal ion, a half equivalent of an alkaline-earth metal ion or a half equivalent of a zinc ion, particularly preferably a hydrogen atom, an ammonium ion, a sodium ion, a potassium ion, ½ calcium ion, ½ magnesium ion or ½ zinc ion.

A most particularly preferred molecular fragment T of formula (PE-1), formula (I) or formula (III) for producing the star polymers according to the present specification obeys the general formula *—B—[(N(CH₂COOM)-B′)_(y)—N(CH₂COOM)₂] in which

-   B denotes a (C₁ to C₆) alkylene residue (preferably ethane-1,2-diyl,     propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl,     butane-1,3-diyl, butane-1,4-diyl), -   B′ denotes a (C₁ to C₆) alkylene residue (preferably     ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl,     butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl) or an N,N-bis(C₁     to C₆) alkylene-N-carboxymethyl, -   M independently of one another, denotes a hydrogen atom or an     equivalent of a monovalent or polyvalent cation, -   y denotes 1 or 2 (preferably 1).

All that has been stated in respect of residue M of the above formula also applies here (see above).

Particularly preferred agents of this example include at least one star polymer comprising at least one polyether having at least one molecular fragment T of said general formula *—B—[(N(CH₂COOM)-B′)_(y)—N(CH₂COOM)₂].

Particularly preferred molecular fragments T from formula (PE-1), formula (I) or formula (III) with the formula *—B—[(N(CH₂COOM)-B′)_(y)—N(CH₂COOM)₂] are selected from at least one representative of the group formed from 3-N-carboxylmethyl-N-(2′-N′,N′-di(carboxymethylamino)ethyl)aminopropyl (B=propane-1,3-diyl, B′=ethane-1,2-diyl, y=1, M as above), 3-N-carboxylmethyl-N-(2′-N′,N′-di(carboxymethylamino)ethyl)-N″-carboxymethylaminoethyl)aminopropyl (B=propane-1,3-diyl, B′=ethane-1,2-diyl, y=2, M as above). 3-N-Carboxylmethyl-N-(2′-N′,N′-di(carboxymethylamino)ethyl)aminopropyl is most particularly preferred.

Most particularly preferred compounds for producing the at least one star polymer according to the present specification are selected from at least one compound of formula (I-1c)

in which

-   A denotes a polyoxyalkylene chain consisting of either ethylene     oxide units or both ethylene oxide and propylene oxide units,     wherein the polyoxyalkylene chain has a maximum proportion of 50 wt.     % of propylene oxide units, relative to the weight of A, -   B denotes a (C₁ to C₆) alkylene residue (preferably ethane-1,2-diyl,     propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl,     butane-1,3-diyl, butane-1,4-diyl), -   B′ denotes a (C₁ to C₆) alkylene residue (preferably     ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl,     butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl) or an N,N-bis(C₁     to C₆) alkylene-N-carboxymethyl, -   M independently of one another, denotes a hydrogen atom or an     equivalent of a monovalent or polyvalent cation, -   R¹ denotes an R³ _(3-x)(R²O)_(x)Si—K— group, in which     -   R² and R³, independently of one another, denote a (C₁ to C₄)         alkyl group (preferably methyl or ethyl),     -   x denotes an integer 1, 2 or 3 (in particular 3),     -   K denotes a connectivity selected from a covalent bond or from a         molecular fragment having two free valences, -   R independently of one another, denotes a (C₁ to C₄) alkyl group     (preferably methyl or ethyl) or a (C₁ to C₆) alkoxy group     (preferably methoxy or ethoxy).

As a compound of formula (III) this compound is preferably reacted with polyether polyols using the method described above to obtain the polyether-modified organic compounds according to the present specification.

The preferred examples in respect of the aforementioned preferred features for A, B, B′, M, R¹ and R apply with the necessary changes in formulae (I-1c) above.

Within the context of this example at least one compound of general formula (III-1) is preferably used as the compound of formula (III) Y—K—Si(OR)_(x)R′_(3-x)  (III-1) in which

-   Y denotes an OH—, NH₂—, NHR— and/or NR₂-reactive group (in     particular an isocyanate group, a halogen atom, a carboxylic acid     anhydride group, a halocarbonyl group (in particular     chlorocarbonyl), an epoxy group, or a formyl group), -   K is defined as for formula (I) (or as for the aforementioned     preferred connectivities), -   R denotes a (C₁ to C₄) alkyl group or a (C₂ to C₄) acyl group (in     particular ethyl or methyl), -   R′ denotes a (C₁ to C₄) alkyl group (in particular methyl or ethyl), -   x denotes 1, 2 or 3.

The compounds of general formula (III-1) include all functional silane derivatives that are capable of reacting with X groups of formula (II). Examples are acrylate silanes such as (3-acryloxypropyl)trimethoxysilane, (acryloxymethyl)triethoxysilane and (acryloxymethyl)methyldimethoxysilane, isocyanato silanes such as (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)triethoxysilane, (isocyanatomethyl)methyldimethoxysilane and (isocyanatomethyl)trimethoxysilane, aldehyde silanes such as triethoxysilylundecanal and triethoxysilylbutyraldehyde, epoxy silanes such as (3-glycidoxypropyl)trimethoxysilane, anhydride silanes such as 3-(triethoxysilyl)propyl succinic acid anhydride, halosilanes such as chloromethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, as well as tetraethyl silicate (TEOS), which is commercially available for example from Wacker Chemie GmbH (Burghausen), Gelest, Inc. (Morrisville, USA) or ABCR GmbH & Co. KG (Karlsruhe) or may be produced by known methods. Isocyanato silanes or anhydride silanes are particularly preferred. If all hydroxyl end groups react completely with isocyanato silanes, completely silylated polyethers are obtained. In such a case the K group includes only the group of atoms located in the starting isocyanato silane between the isocyanato group and the silyl group. If all hydroxyl end groups react completely with anhydride silanes, for example 3-(triethoxysilyl)propyl succinic acid anhydride, completely silylated polyethers are likewise obtained. In such a case the K′ group includes only the group of atoms located in the starting anhydride silane between the anhydride group and the silyl group.

If the residues X and X′ in general formula (II) denote OH, NH₂ or NHR, the reaction with the compounds of general formula (III) or (III-1) may take place either with cleavage of the HY compound—as for example in the case of the reaction of an OH group with a monohalosilane (K=direct bond)—or with addition—as for example in the case of the reaction of an OH group with an isocyanatoalkyl silane (formation of a urethane).

The residues X and X′ of formula (II) preferably (and independently of one another) denote OH, NH₂ and NHR, particularly preferable are OH and NH₂.

The residue R in the NHR, NR₂ and OR groups of formula (III-1) preferably denotes a linear or branched alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms.

In the reaction between the compounds of formula (I) and the compounds of formula (II), at least one hydrogen atom, preferably up to four hydrogen atoms of the OH and/or NH₂ groups, are each reacted with a molecule of the compound of general formula (II), such that at least monosilylated, in the case of the diamino compounds of general formula (I) up to tetrasilylated, polyethers are formed.

Most particularly preferred polyethers for producing the star polymers according to the present specification are selected from at least one compound of formula (I-1 a) or (I-1b)

in which

-   A denotes a polyoxyalkylene chain consisting of either ethylene     oxide units or both ethylene oxide and propylene oxide units,     wherein the polyoxyalkylene chain has a maximum proportion of 50 wt.     % of propylene oxide units, relative to the weight of A, -   R and R″ independently of one another, denote methylene,     ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl,     butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, phenylene, -   R¹ denotes a (C₁ to C₆) alkyl group, a hydrogen atom or an R³     _(3-x)(R²O)_(x)Si—K— group, -   R² denotes a (C₁ to C₄) alkyl group (preferably methyl or ethyl), -   R³ denotes a (C₁ to C₆) alkyl group or an aryl group (preferably     methyl), -   x denotes 1, 2 or 3 (in particular 3).

Within the context of a further example of the present specification, said star polymer has as the center a solid particle which is surface-modified with at least three *—K′-A-K-T residues, in which

-   A denotes a polyoxyalkylene chain consisting of either ethylene     oxide units or both ethylene oxide and propylene oxide units,     wherein the polyoxyalkylene chain has a maximum proportion of 50 wt.     % of propylene oxide units, relative to the weight of A, -   K and K′ independently of one another, denote a connectivity     selected from a covalent bond or from a molecular fragment having     two free valences, -   T denotes a structural fragment comprising at least one of the     following:     -   at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′,         independently of one another, denote a (C₁ to C₄) alkyl group         (in particular methyl or ethyl), x denotes 1, 2 or 3, or     -   at least one anionic group, or     -   at least one quaternized nitrogen atom.

The skeleton of the solid particles is preferably selected from aluminates, silicates, aluminum silicates, zinc oxide, titanium dioxide and SiO₂, in particular from aluminates, silicates, aluminum silicates and silica gel. Mixtures of these preferred or particularly preferred solids particles are likewise in accordance with the present specification.

Particularly preferred aluminates are selected from alpha-aluminum oxide, beta-aluminum oxide, gamma-aluminum oxide and mixtures thereof.

Particularly preferred aluminum silicates (also known as alumosilicates) are selected from phyllosilicates, and tectosilicates.

Preferably suitable phyllosilicates are selected from kaolins (in particular from kaolinite, dickite, hallosite and nacrite), serpentine, talc, pyrophyllite, montmorillonite, quartz, bentonite, mica (in particular from illite, muscovite, paragonite, phlogopite, biotite, lepidolite, margarite, and smectite (in particular from montmorillonite, saponite, nontronite, and hectorite)).

Preferably suitable tectosilicates are selected from feldspar minerals (in particular albite, orthoclase, anorthite, leucite, sodalite, hauyne, labradorite, lazurite, nosean, nepheline), and zeolites.

Zeolites are natural or synthetic crystalline aluminum silicates of alkali or alkaline-earth metals. Zeolites consist of SiO₄ and AlO₄ tetrahedra, which are connected by four-, six-, eight- or twelve-membered oxygen rings, giving rise to cavities which extend throughout the entire zeolite crystal. The preferred zeolites include zeolites of type A, K, L, P-L, O, T, X, Y and Ω as well as mixtures thereof. Particularly preferred zeolites are selected in particular from zeolite A (in particular from Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]), Ca₅Na₅[(AlO₂)₁₂(SiO₂)₁₂], [K₁₂[(AlO₂)₁₂(SiO₂)₁₂]), zeolite X (in particular from Na₈₆[(AlO₂)₈₆(SiO₂)₁₀₆]), Ca₄₀Na₆[(AlO₂)₈₆(SiO₂)₁₀₆)], Sr₂₁Ba₂₂[(AlO₂)₈₆(SiO₂)₁₀₆]), zeolite Y (in particular from Na₅₆[(AlO₂)₅₆(SiO₂)₁₃₆], Na₅₆[(AlO₂)₅₆(SiO₂)₁₃₆]), ZSM-5 (in particular from Na₃[(AlO₂)₃(SiO₂)₉₃]), mordenite, and silicalite (SiO₂)₉₆.

For the residues A, K, K′ and T the preferred examples listed under formula (PE-1) apply.

Cosmetic agents are preferred according to the present specification which include, in a cosmetically acceptable carrier,

-   (a) at least one star polymer in the form of a polyether-modified     solid particle obtained by reacting hydroxyl group-containing solid     particles with at least one polyether of formula (I)     T-K′-A-K′-T′  (I)     -   in which

A denotes a polyoxyalkylene chain consisting of either ethylene oxide units or both ethylene oxide and propylene oxide units, wherein the polyoxyalkylene chain has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of A,

-   -   K and K′ independently of one another, denote a connectivity         selected from a covalent bond or from a molecular fragment         having two free valences,     -   T and T′ independently of one another, denote a molecular         fragment comprising         -   at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and             R′, independently of one another, denote a (C₁ to C₄) alkyl             group (preferably methyl or ethyl), x denotes 1, 2 or 3, or         -   at least one anionic group, or         -   at least one quaternized nitrogen atom,     -    wherein at most one residue from T or T′ may additionally         denote a (C₁ to C₆) alkyl group, an aryl group, an aryl (C₁ to         C₆) alkyl group, a (C₁ to C₆) alkoxy group or a (C₂ to C₆) acyl         group,

-   and

-   (b) at least one coloring compound.

The star polymers in the form of a polyether-modified solid particle are preferably included in the agents according to the present specification in an amount from 0.01 to 15.0 wt. %, preferably from 0.1 to 8.0 wt. %, particularly preferably 0.2 to 5.0 wt. %, most preferably from 0.25 to 2.5 wt. %, relative in each case to the weight of the total agent.

The coloring compounds within the meaning of the present specification are preferably selected from:

-   (1) at least one oxidation dye precursor of the developer component     type and optionally additionally at least one coupler component -   and/or -   (2) at least one substantive dye -   and/or -   (3) at least one precursor of nature-analogous dyes.

It is preferable according to the present specification to use a p-phenylenediamine derivative or one of its physiologically acceptable salts as the developer component. p-Phenylenediamine derivatives of formula (E1) are particularly preferred

in which

-   -   G¹ denotes a hydrogen atom, a (C₁ to C₄) alkyl residue, a (C₁ to         C₄) monohydroxyalkyl residue, a (C₂ to C₄) polyhydroxyalkyl         residue, a (C₁ to C₄) alkoxy (C₁ to C₄) alkyl residue, a         4′-aminophenyl residue or a (C₁ to C₄) alkyl residue, which is         substituted with a nitrogen-containing group, a phenyl residue         or a 4′-aminophenyl residue;     -   G² denotes a hydrogen atom, a (C₁ to C₄) alkyl residue, a (C₁ to         C₄) monohydroxyalkyl residue, a (C₂ to C₄) polyhydroxyalkyl         residue, a (C₁ to C₄) alkoxy (C₁ to C₄) alkyl residue or a (C₁         to C₄) alkyl residue, which is substituted with a         nitrogen-containing group;     -   G³ denotes a hydrogen atom, a halogen atom, such as a chlorine,         bromine, iodine or fluorine atom, a (C₁ to C₄) alkyl residue, a         (C₁ to C₄) monohydroxyalkyl residue, a (C₂ to C₄)         polyhydroxyalkyl residue, a (C₁ to C₄) hydroxyalkyl residue, a         (C₁ to C₄) alkoxy (C₁ to C₄) alkyl residue, a (C₁ to C₄) acetyl         aminoalkoxy residue, a mesylamino (C₁ to C₄) alkoxy residue or a         (C₁ to C₄) carbamoyl aminoalkoxy residue;     -   G⁴ denotes a hydrogen atom, a halogen atom, a (C₁ to C₄) alkyl         residue or a (C₁ to C₄) alkoxy (C₁ to C₄) alkyl residue, or     -   if G³ and G⁴ are in ortho-position to one another, they may         together form a bridging α,ω-alkylene dioxo group, such as for         example an ethylene dioxy group.

Particularly preferred p-phenylenediamines of formula (E1) are selected from p-phenylenediamine, p-toluylenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-3-methyl-(N,N-diethyl)aniline, N,N-bis-(β-hydroxyethyl)-p-phenylenediamine, 4-N,N-bis-(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis-(β-hydroxyethyl)-amino-2-chloroaniline, 2-(β-hydroxyethyl)-p-phenylenediamine, 2-(α,β-dihydroxyethyl)-p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N-(β-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl-3-methyl-p-phenylenediamine, N,N-(ethyl,β-hydroxyethyl)-p-phenylenediamine, N-(β,γ-dihydroxypropyl)-p-phenylenediamine, N-(β-aminophenyl)-p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-(β-hydroxyethyloxy)-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, 2-(β-acetylaminoethyloxy)-p-phenylenediamine, N-(β-methoxyethyl)-p-phenylenediamine, N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine, 5,8-diaminobenzo-1,4-dioxane as well as the physiologically acceptable salts thereof.

Most particularly preferred p-phenylenediamine derivatives of formula (E1)) according to the present specification are selected from at least one compound of the group p-phenylenediamine, p-toluylenediamine, 2-(β-hydroxyethyl)-p-phenylenediamine, 2-(α,β-dihydroxyethyl)-p-phenylenediamine, N,N-bis-(β-hydroxyethyl)-p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine, as well as the physiologically acceptable salts of these compounds.

It may be preferable according to the present specification to use as the developer component compounds including at least two aromatic nuclei which are substituted with amino and/or hydroxyl groups.

Of the binuclear developer components which may be used in the coloring compositions according to the present specification, the compounds corresponding to the following formula (E2) and the physiologically acceptable salts thereof may be cited in particular:

in which:

-   -   Z¹ and Z², independently of one another, denote a hydroxyl or         NH₂ residue, which is optionally substituted by a (C₁ to C₄)         alkyl residue, by a (C₁ to C₄) hydroxyalkyl residue and/or by a         bridge Y or which is optionally part of a bridging ring system,     -   the bridge Y denotes an alkylene group having 1 to 14 carbon         atoms, such as for example a linear or branched alkylene chain         or alkylene ring, which may be interrupted or terminated by one         or more nitrogen-containing groups and/or by one or more         heteroatoms such as oxygen, sulfur or nitrogen atoms and may         optionally be substituted by one or more hydroxyl or (C₁ to C₈)         alkoxy residues, or a direct bond,     -   G⁵ and G⁶, independently of one another, denote a hydrogen or         halogen atom, a (C₁ to C₄) alkyl residue, a (C₁ to C₄)         monohydroxyalkyl residue, a (C₂ to C₄) polyhydroxyalkyl residue,         a (C₁ to C₄) aminoalkyl residue or a direct bond to the bridge         Y,     -   G⁷, G⁸, G⁹, G¹⁰, G¹¹ and G¹², independently of one another,         denote a hydrogen atom, a direct bond to the bridge Y or a (C₁         to C₄) alkyl residue,         with the proviso that the compounds of formula (E2) include only         one bridge Y per molecule.

The substituents used in formula (E2) are defined according to the present specification in an analogous manner to the above statements.

Preferred binuclear developer components of formula (E2) are selected in particular from at least one of the following compounds: N,N′-bis-(α-hydroxyethyl)-N,N′-bis-(4′-aminophenyl)-1,3-diaminopropan-2-ol, N,N′-bis-(β-hydroxyethyl)-N,N′-bis-(4′-aminophenyl)ethylenediamine, N,N′-bis-(4′-aminophenyl)tetramethylenediamine, N,N′-bis-(β-hydroxyethyl)-N,N′-bis-(4′-aminophenyl)tetramethylenediamine, N,N′-bis-(4-(methylamino)phenyl)tetramethylenediamine, N,N′-diethyl-N,N′-bis-(4′-amino-3′-methylphenyl)ethylenediamine, bis-(2-hydroxy-5-aminophenyl)methane, N,N′-bis-(4′-aminophenyl)-1,4-diazacycloheptane, N,N′-bis-(2-hydroxy-5-aminobenzyl)piperazine, N-(4′-aminophenyl)-p-phenylenediamine and 1,10-bis-(2′,5′-diaminophenyl)-1,4,7,10-tetraoxadecane as well as the physiologically acceptable salts thereof.

Most particularly preferred binuclear developer components of formula (E2) are selected from N,N′-bis-(β-hydroxyethyl)-N,N′-bis-(4-aminophenyl)-1,3-diaminopropan-2-ol, bis-(2-hydroxy-5-aminophenyl)methane, 1,3-bis-(2,5-diaminophenoxy)propan-2-ol, N,N′-bis-(4-aminophenyl)-1,4-diazacycloheptane, 1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane or one of the physiologically acceptable salts of these compounds.

It is furthermore preferable according to the present specification to use at least one p-aminophenol derivative or one of the physiologically acceptable salts thereof as the developer component. p-Aminophenol derivatives of formula (E3) are particularly preferred

in which:

-   -   G¹³ denotes a hydrogen atom, a halogen atom, a (C₁ to C₄) alkyl         residue, a (C₁ to C₄) monohydroxyalkyl residue, a (C₂ to C₄)         polyhydroxyalkyl residue, a (C₁ to C₄) alkoxy (C₁ to C₄) alkyl         residue, a (C₁ to C₄) aminoalkyl residue, a hydroxy (C₁ to C₄)         alkylamino residue, a (C₁ to C₄) hydroxyalkoxy residue, a (C₁ to         C₄) hydroxyalkyl (C₁ to C₄) aminoalkyl residue or a (di-[(C₁ to         C₄) alkyl]amino) (C₁ to C₄) alkyl residue, and     -   G¹⁴ denotes a hydrogen or halogen atom, a (C₁ to C₄) alkyl         residue, a (C₁ to C₄) monohydroxyalkyl residue, a (C₂ to C₄)         polyhydroxyalkyl residue, a (C₁ to C₄) alkoxy (C₁ to C₄) alkyl         residue, a (C₁ to C₄) aminoalkyl residue or a (C₁ to C₄)         cyanoalkyl residue,     -   G¹⁵ denotes hydrogen, a (C₁ to C₄) alkyl residue, a (C₁ to C₄)         monohydroxyalkyl residue, a (C₂ to C₄) polyhydroxyalkyl residue,         a phenyl residue or a benzyl residue, and     -   G¹⁶ denotes hydrogen or a halogen atom.

The substituents used in formula (E3) are defined according to the present specification in an analogous manner to the above statements.

Preferred p-aminophenols of formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-(β-hydroxyethoxy)phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethyl aminomethyl)phenol, 4-amino-2-(α,β-dihydroxyethyl)phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2-(diethylaminomethyl)phenol as well as the physiologically acceptable salts thereof.

Most particularly preferred compounds of formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(α,β-di hydroxyethyl)phenol and 4-amino-2-(diethylaminomethyl)phenol.

The developer component may further be selected from o-aminophenol and derivatives thereof, such as for example 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

The developer component may furthermore preferably be selected from heterocyclic developer components, such as for example from pyrimidine derivatives, pyrazole derivatives or the physiologically acceptable salts thereof.

Preferred pyrimidine derivatives are selected according to the present specification from compounds according to formula (E4) or the physiologically acceptable salts thereof,

in which

-   -   G¹⁷, G¹⁸ and G¹⁹, independently of one another, denote a         hydrogen atom, a hydroxyl group, a (C₁ to C₄) alkoxy group or an         amino group, and     -   G²⁰ denotes a hydroxyl group or an —NG²¹G²² group, in which G²¹         and G²², independently of one another, denote a hydrogen atom, a         (C₁ to C₄) alkyl group, or a (C₁ to C₄) monohydroxyalkyl group,         with the proviso that at most two of the groups out of G¹⁷, G¹⁸,         G¹⁹ and G²⁰ denote a hydroxyl group and at most two of the         residues G¹⁷, G¹⁸ and G¹⁹ denote a hydrogen atom. It is in turn         preferable if according to formula (E4) at least two groups out         of G¹⁷, G¹⁸, G¹⁹ and G²⁰ denote an —NG²¹G²² group and at most         two groups out of G¹⁷, G¹⁸, G¹⁹ and G²⁰ denote a hydroxyl group.

Particularly preferred pyrimidine derivatives are in particular the compounds 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are selected according to the present specification from compounds according to formula (E5),

in which

-   -   G²³, G²⁴, G²⁵, independently of one another, denote a hydrogen         atom, a (C₁ to C₄) alkyl group, a (C₁ to C₄) monohydroxyalkyl         group, a (C₂ to C₄) polyhydroxyalkyl group, an optionally         substituted aryl group or an optionally substituted aryl (C₁ to         C₄) alkyl group, with the proviso that if G²⁵ denotes a hydrogen         atom, G²⁷ in addition to the above groups may also denote an         —NH₂ group,     -   G²⁶ denotes a hydrogen atom, a (C₁ to C₄) alkyl group, a (C₁ to         C₄) monohydroxyalkyl group or a (C₂ to C₄) polyhydroxyalkyl         group, and     -   G²⁷ denotes a hydrogen atom, an optionally substituted aryl         group, a (C₁ to C₄) alkyl group or a (C₁ to C₄) monohydroxyalkyl         group, in particular a hydrogen atom or a methyl group.

In formula (E5) the residue —NG²⁵G²⁶ preferably binds to the 5-position and the residue G²⁷ to the 3-position of the pyrazole cycle.

Particularly preferred pyrazole derivatives are in particular the compounds selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(β-aminoethyl)amino-1,3-dimethylpyrazole, as well as the physiologically acceptable salts thereof.

Examples of the residues cited as substituents of the compounds of formulae (E1) to (E5) are listed below: Examples of (C₁ to C₄) alkyl residues are the groups —CH₃, —CH₂CH₃, —CH₂CH₂CH₃, —CH(CH₃)₂, —CH₂CH₂CH₂CH₃, —CH₂CH(CH₃)₂, —CH(CH₃)CH₂CH₃, —C(CH₃)₃. Examples according to the present specification of (C₁ to C₄) alkoxy residues are —OCH₃, —OCH₂CH₃, —OCH₂CH₂CH₃, —OCH(CH₃)₂, —OCH₂CH₂CH₂CH₃, —OCH₂CH(CH₃)₂, —OCH(CH₃)CH₂CH₃, —OC(CH₃)_(3-x) in particular a methoxy or an ethoxy group.

Preferred examples of a (C₁ to C₄) monohydroxyalkyl group are furthermore —CH₂OH, —CH₂CH₂OH, —CH₂CH₂CH₂OH, —CHCH(OH)CH₃, —CH₂CH₂CH₂CH₂OH, the —CH₂CH₂OH group being preferred. A particularly preferred example of a (C₂ to C₄) polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms are F, Cl or Br atoms, Cl atoms being most particularly preferred examples. Examples of nitrogen-containing groups are in particular —NH₂, (C₁ to C₄) monoalkylamino groups, (C₁ to C₄) dialkylamino groups, (C₁ to C₄) trialkylammonium groups, (C₁ to C₄) monohydroxyalkyl amino groups, imidazolinium and —NH₃ ⁺. Examples of (C₁ to C₄) monoalkylamino groups are —NHCH₃, —NHCH₂CH₃, —NHCH₂CH₂CH₃, —NHCH(CH₃)₂.

Examples of (C₁ to C₄) dialkylamino groups are —N(CH₃)₂, —N(CH₂CH₃)₂. Examples of (C₁ to C₄) trialkylammonium groups are —N⁺(CH₃)₃, —N⁺(CH₃)₂(CH₂CH₃), —N⁺(CH₃)(CH₂CH₃)₂.

Examples of (C₁ to C₄) hydroxyalkylamino residues are —NH—CH₂CH₂OH, —NH—CH₂CH₂OH, —NH—CH₂CH₂CH₂OH, —NH—CH₂CH₂CH₂OH. Examples of (C₁ to C₄) alkoxy (C₁ to C₄) alkyl groups are the groups —CH₂CH₂—O—CH₃, —CH₂CH₂CH₂—O—CH₃, —CH₂CH₂—O—CH₂CH₃, —CH₂CH₂CH₂—O—CH₂CH₃, —CH₂CH₂—O—CH(CH₃), —CH₂CH₂CH₂—O—CH(CH₃).

Examples of hydroxy (C₁ to C₄) alkoxy residues are —O—CH₂OH, —O—CH₂CH₂OH, —O—CH₂CH₂CH₂OH, —O—CHCH(OH)CH₃, —O—CH₂CH₂CH₂CH₂OH. Examples of (C₁ to C₄) acetylaminoalkoxy residues are —O—CH₂NHC(O)CH₃, —O—CH₂CH₂NHC(O)CH₃, —O—CH₂CH₂CH₂NHC(O)CH₃, —O—CH₂CH(NHC(O)CH₃)CH₃, —O—CH₂CH₂CH₂CH₂NHC(O)CH₃. Examples of (C₁ to C₄) carbamoylaminoalkoxy residues are —O—CH₂CH₂—NH—C(O)—NH₂, —O—CH₂CH₂CH₂—NH—C(O)—NH₂, —O—CH₂CH₂CH₂CH₂—NH—C(O)—NH₂. Examples of (C₁ to C₄) aminoalkyl residues are —CH₂NH₂, —CH₂CH₂NH₂, —CH₂CH₂CH₂NH₂, —CH₂CH(NH₂)CH₃, —CH₂CH₂CH₂CH₂NH₂.

Examples of (C₁ to C₄) cyanoalkyl residues are —CH₂CN, —CH₂CH₂CN, —CH₂CH₂CH₂CN.

Examples of (C₁ to C₄) hydroxyalkylamino (C₁ to C₄) alkyl residues are —CH₂CH₂NH—CH₂CH₂OH, —CH₂CH₂CH₂NH—CH₂CH₂OH, —CH₂CH₂NH—CH₂CH₂CH₂OH, —CH₂CH₂CH₂NH—CH₂CH₂CH₂OH.

Examples of di[(C₁ to C₄) hydroxyalkyl]amino (C₁ to C₄) alkyl residues are —CH₂CH₂N(CH₂CH₂OH)₂, —CH₂CH₂CH₂N(CH₂CH₂OH)₂, —CH₂CH₂N(CH₂CH₂CH₂OH)₂, —CH₂CH₂CH₂N(CH₂CH₂CH₂OH)₂. An example of aryl groups is the phenyl group.

Examples of aryl (C₁ to C₄) alkyl groups are the benzyl group and the 2-phenylethyl group.

Coupler components within the meaning of the present specification permit at least one substitution of a chemical residue of the coupler with the oxidized form of the developer component. A covalent bond forms between the coupler and developer component in this process. Couplers are preferably cyclic compounds bearing at least two functional groups on the at least one ring, selected from (i) optionally substituted amino groups and/or (ii) hydroxyl groups. If the cyclic compound is a six-membered ring (preferably aromatic), said groups are preferably in ortho-position or meta-position to one another.

Coupler components according to the present specification are preferably selected as at least one compound from one of the following classes:

-   -   m-aminophenol and/or derivatives thereof,     -   m-diaminobenzene and/or derivatives thereof,     -   o-diaminobenzene and/or derivatives thereof,     -   o-aminophenol derivatives, such as for example o-aminophenol,     -   naphthalene derivatives having at least one hydroxyl group,     -   di- or trihydroxybenzene and/or derivatives thereof,     -   pyridine derivatives,     -   pyrimidine derivatives,     -   monohydroxyindole derivatives and/or monoaminoindole         derivatives,     -   monohydroxyindoline derivatives and/or monoaminoindoline         derivatives,     -   pyrazolone derivatives such as for example         1-phenyl-3-methylpyrazol-5-one,     -   morpholine derivatives such as for example         6-hydroxybenzomorpholine or 6-aminobenzomorpholine,     -   quinoxaline derivatives such as for example         6-methyl-1,2,3,4-tetrahydroquinoxaline.         Within the context of this example mixtures of two or more         compounds from one or more of these classes are likewise in         accordance with the present specification.

The m-aminophenols or derivatives thereof for use according to the present specification are preferably selected from at least one compound of formula (K1) and/or from at least one physiologically acceptable salt of a compound according to formula (K1),

in which

-   G¹ and G² independently of one another, denote a hydrogen atom, a     (C₁ to C₄) alkyl group, a (C₃ to C₆) cycloalkyl group, a (C₂ to C₄)     alkenyl group, a (C₁ to C₄) monohydroxyalkyl group, a (C₂ to C₄)     polyhydroxyalkyl group, a (C₂ to C₄) perfluoroacyl group, an aryl     (C₁ to C₆) alkyl group, an amino (C₁ to C₆) alkyl group, a (C₁ to     C₆) dialkylamino (C₁ to C₆) alkyl group or a (C₁ to C₆) alkoxy (C₁     to C₆) alkyl group, wherein G¹ and G² together with the nitrogen     atom may form a five-membered, six-membered or seven-membered ring, -   G³ and G⁴ independently of one another, denote a hydrogen atom, a     halogen atom, a (C₁ to C₄) alkyl group, a (C₁ to C₄) alkoxy group, a     hydroxyl group, a (C₁ to C₄) monohydroxyalkyl group, a (C₂ to C₄)     polyhydroxyalkyl group, a hydroxy (C₁ to C₄) alkoxy group, a (C₁ to     C₆) alkoxy (C₂ to C₆) alkoxy group, an aryl group or a heteroaryl     group.

Particularly preferred m-aminophenol coupler components are selected from at least one compound from the group which is formed from m-aminophenol, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-(2′-hydroxyethyl)amino-2-methylphenol, 3-(diethylamino)phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-(methylamino)benzene, 3-ethylamino-4-methylphenol, 2,4-dichloro-3-aminophenol and the physiologically acceptable salts of all aforementioned compounds.

The m-diaminobenzenes or derivatives thereof for use according to the present specification are preferably selected from at least one compound of formula (K2) and/or from at least one physiologically acceptable salt of a compound according to formula (K2),

in which

-   G⁵, G⁶, G′ and G⁸ independently of one another, denote a hydrogen     atom, a (C₁ to C₄) alkyl group, a (C₃ to C₆) cycloalkyl group, a (C₂     to C₄) alkenyl group, a (C₁ to C₄) monohydroxyalkyl group, a (C₂ to     C₄) polyhydroxyalkyl group, a (C₁ to C₄) alkoxy (C₁ to C₄) alkyl     group, an aryl (C₁ to C₄) alkyl group, a heteroaryl (C₁ to C₄) alkyl     group, a (C₂ to C₄) perfluoroacyl group or together with the     nitrogen atom form a five-membered or six-membered heterocycle -   G⁹ and G¹⁰ independently of one another, denote a hydrogen atom, a     halogen atom, a (C₁ to C₄) alkyl group, a ω-(2,4-diaminophenyl) (C₁     to C₄) alkyl group, a ω-(2,4-diaminophenyloxy) (C₁ to C₄) alkoxy     group, a (C₁ to C₄) alkoxy group, a hydroxyl group, a (C₁ to C₄)     alkoxy (C₂ to C₄) alkoxy group, an aryl group, a heteroaryl group, a     (C₁ to C₄) monohydroxyalkyl group, a (C₂ to C₄) polyhydroxyalkyl     group, a hydroxy (C₁ to C₄) alkoxy group.

Particularly preferred m-diaminobenzene coupler components are selected from at least one compound from the group which is formed from m-phenylenediamine, 2-(2,4-diaminophenoxy)ethanol, 1,3-bis(2,4-diaminophenoxy)propane, 1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene, 1,3-bis(2,4-diaminophenyl)propane, 2,6-bis(2′-hydroxyethylamino)-1-methylbenzene, 2-({3-[(2-hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-hydroxyethyl)amino]-4,5-dimethylphenyl}amino)ethanol, 2-[3-morpholin-4-ylphenyl)amino]ethanol, 3-amino-4-(2-methoxyethoxy)-5-methylphenylamine, 1-amino-3-bis-(2′-hydroxyethyl)aminobenzene and the physiologically acceptable salts of all aforementioned compounds.

The o-diaminobenzenes or derivatives thereof for use according to the present specification are preferably selected from at least one compound of formula (K3) and/or from at least one physiologically acceptable salt of a compound according to formula (K3),

in which

-   G¹¹, G¹², G¹³, and G¹⁴ independently of one another, denote a     hydrogen atom, a (C₁ to C₄) alkyl group, a (C₃ to C₆) cycloalkyl     group, a (C₂ to C₄) alkenyl group, a (C₁ to C₄) monohydroxyalkyl     group, a (C₂ to C₄) polyhydroxyalkyl group, a (C₁ to C₄) alkoxy (C₁     to C₄) alkyl group, an aryl (C₁ to C₄) alkyl group, a heteroaryl (C₁     to C₄) alkyl group, a (C₂ to C₄) perfluoroacyl group or together     with the nitrogen atom form a five-membered or six-membered     heterocycle -   G¹⁵ and G¹⁶ independently of one another, denote a hydrogen atom, a     halogen atom, a carboxyl group, a (C₁ to C₄) alkyl group, a (C₁ to     C₄) alkoxy group, a hydroxyl group, a (C₁ to C₄) monohydroxyalkyl     group, a (C₂ to C₄) polyhydroxyalkyl group, a hydroxy (C₁ to C₄)     alkoxy group.

Particularly preferred o-diaminobenzene coupler components are selected from at least one compound from the group formed from 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all aforementioned compounds.

Preferred di- or trihydroxybenzenes and derivatives thereof are selected from at least one compound of the group formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene.

The pyridine derivatives for use according to the present specification are preferably selected from at least one compound of formula (K4) and/or from at least one physiologically acceptable salt of a compound according to formula (K4),

in which

-   G¹⁷ and G¹⁸ independently of one another, denote a hydroxyl group or     an —NG²¹G²² group,     -   in which G²¹ and G²², independently of one another, denote a         hydrogen atom, a (C₁ to C₄) alkyl group, a (C₃ to C₆) cycloalkyl         group, a (C₂ to C₄) alkenyl group, an aryl group, a (C₁ to C₄)         monohydroxyalkyl group, a (C₂ to C₄) polyhydroxyalkyl group, a         (C₁ to C₄) alkoxy (C₁ to C₄) alkyl group, an aryl (C₁ to C₄)         alkyl group, a heteroaryl (C₁ to C₄) alkyl group, -   G¹⁹ and G²⁰ independently of one another, denote a hydrogen atom, a     halogen atom, a (C₁ to C₄) alkyl group or a (C₁ to C₄) alkoxy group.

It is preferable if according to formula (K4) the residues G¹⁷ and G¹⁸ are in ortho-position or meta-position to one another.

Particularly preferred pyridine derivatives are selected from at least one compound of the group formed from 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 3,4-diaminopyridine, 2-(2-methoxyethyl)amino-3-amino-6-methoxypyridine, 2-(4′-methoxyphenyl)amino-3-aminopyridine, and the physiologically acceptable salts of the aforementioned compounds.

Preferred naphthalene derivatives including at least one hydroxyl group are selected from at least one compound of the group which is formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene.

The indole derivatives for use according to the present specification are preferably selected from at least one compound of formula (K5) and/or from at least one physiologically acceptable salt of a compound according to formula (K5),

in which

-   G²³ denotes a hydrogen atom, a (C₁ to C₄) alkyl group, a (C₃ to C₆)     cycloalkyl group, a (C₂ to C₄) alkenyl group, a (C₁ to C₄)     monohydroxyalkyl group, a (C₂ to C₄) polyhydroxyalkyl group, an aryl     (C₁ to C₄) alkyl group, -   G²⁴ denotes a hydroxyl group or an —NG²⁶G²⁷ group, in which G²⁶ and     G²⁷, independently of one another, denote a hydrogen atom, a (C₁ to     C₄) alkyl group, a (C₃ to C₆) cycloalkyl group, a (C₂ to C₄) alkenyl     group, a (C₁ to C₄) monohydroxyalkyl group, a (C₂ to C₄)     polyhydroxyalkyl group, -   G²⁵ denotes a hydrogen atom, a halogen atom or a (C₁ to C₄) alkyl     group,     with the proviso that G²⁴ binds in meta-position or ortho-position     to the structural fragment NG²³ of the formula.

Particularly preferred indole derivatives are selected from at least one compound of the group formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable salts of the aforementioned compounds.

The indoline derivatives for use according to the present specification are preferably selected from at least one compound of formula (K6) and/or from at least one physiologically acceptable salt of a compound according to formula (K6),

in which

-   G²⁸ denotes a hydrogen atom, a (C₁ to C₄) alkyl group, a (C₃ to C₆)     cycloalkyl group, a (C₂ to C₄) alkenyl group, a (C₁ to C₄)     monohydroxyalkyl group, a (C₂ to C₄) polyhydroxyalkyl group, an aryl     (C₁ to C₄) alkyl group, -   G²⁹ denotes a hydroxyl group or an —NG³¹G³² group, in which G³¹ and     G³², independently of one another, denote a hydrogen atom, a (C₁ to     C₄) alkyl group, a (C₃ to C₆) cycloalkyl group, a (C₂ to C₄) alkenyl     group, a (C₁ to C₄) monohydroxyalkyl group, a (C₂ to C₄)     polyhydroxyalkyl group, -   G³⁰ denotes a hydrogen atom, a halogen atom or a (C₁ to C₄) alkyl     group,     with the proviso that G²⁹ binds in meta-position or ortho-position     to the structural fragment NG²⁸ of the formula.

Particularly preferred indoline derivatives are selected from at least one compound of the group formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and the physiologically acceptable salts of the aforementioned compounds.

Preferred pyrimidine derivatives are selected from at least one compound of the group formed from 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-tri hydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine and the physiologically acceptable salts of the aforementioned compounds.

Particularly preferred coupler components according to the present specification are selected from m-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol, 5-(2′-hydroxyethyl)amino-2-methylphenol, 2,4-dichloro-3-aminophenol, o-aminophenol, m-phenylenediamine, 2-(2,4-diaminophenoxy)ethanol, 1,3-bis(2,4-diaminophenoxy)propane, 1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene, 1,3-bis(2,4-diaminophenyl)propane, 2,6-bis(2′-hydroxyethylamino)-1-methylbenzene, 2-({3-[(2-hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol, 2-({3-[(2-hydroxyethyl)amino]-4,5-dimethylphenyl}amino)ethanol, 2-[3-morpholin-4-ylphenyl)amino]ethanol, 3-amino-4-(2-methoxyethoxy)-5-methylphenylamine, 1-amino-3-bis-(2′-hydroxyethyl)aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of the aforementioned compounds.

The coupler components are preferably used in an amount from 0.005 to 20 wt. %, preferably 0.1 to 5 wt. %, relative in each case to the ready-to-use oxidation coloring agent.

Developer components and coupler components may be used in approximately molar amounts to one another. Even if the molar use has proved convenient, a certain excess of individual oxidation dye precursors is not disadvantageous, such that developer components and coupler components may be in a molar ratio of 1:0.5 to 1:3, in particular 1:1 to 1:2.

Examples of the residues cited as substituents of the compounds of formulae (K1) to (K6) are listed below: Examples of (C₁ to C₄) alkyl residues are the —CH₃, —CH₂CH₃, —CH₂CH₂CH₃, —CH(CH₃)₂, —CH₂CH₂CH₂CH₃, —CH₂CH(CH₃)₂, —CH(CH₃)CH₂CH₃, —C(CH₃)₃ groups.

Examples according to the present specification of (C₃ to C₆) cycloalkyl groups are the cyclopropyl, the cyclopentyl and the cyclohexyl group. Examples according to the present specification of (C₁ to C₄) alkoxy residues are —OCH₃, —OCH₂CH₃, —OCH₂CH₂CH₃, —OCH(CH₃)₂, —OCH₂CH₂CH₂CH₃, —OCH₂CH(CH₃)₂, —OCH(CH₃)CH₂CH₃, —OC(CH₃)_(3-x) in particular a methoxy or an ethoxy group.

Furthermore, —CH₂OH, —CH₂CH₂OH, —CH₂CH₂CH₂OH, —CH₂CH(OH)CH₃, —CH₂CH₂CH₂CH₂OH may be cited as preferred examples of a (C₁ to C₄) monohydroxyalkyl group, the —CH₂CH₂OH group being preferred.

A particularly preferred example of a (C₂ to C₄) polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms are F, Cl or Br atoms, Cl atoms being most particularly preferred examples. Examples of nitrogen-containing groups are in particular —NH₂, (C₁ to C₄) monoalkylamino groups, (C₁ to C₄) dialkylamino groups, (C₁ to C₄) trialkylammonium groups, (C₁ to C₄) monohydroxyalkyl amino groups, imidazolinium and —NH₃ ⁺. Examples of (C₁ to C₄) monoalkylamino groups are —NHCH₃, —NHCH₂CH₃, —NHCH₂CH₂CH₃, —NHCH(CH₃)₂. Examples of (C₁ to C₄) dialkylamino groups are —N(CH₃)₂, —N(CH₂CH₃)₂. Examples of (C₁ to C₄) alkoxy (C₁ to C₄) alkyl groups are the groups —CH₂CH₂—O—CH₃, —CH₂CH₂CH₂—O—CH₃, —CH₂CH₂—O—CH₂CH₃, —CH₂CH₂CH₂—O—CH₂CH₃, —CH₂CH₂—O—CH(CH₃)₂, —CH₂CH₂CH₂—O—CH(CH₃)₂.

Examples of (C₁ to C₄) alkoxy (C₁ to C₄) alkoxy groups are the groups —O—CH₂CH₂—O—CH₃, —O—CH₂CH₂CH₂—O—CH₃, —O—CH₂CH₂—O—CH₂CH₃, —O—CH₂CH₂CH₂—O—CH₂CH₃, —O—CH₂CH₂—O—CH(CH₃)₂, —O—CH₂CH₂CH₂—O—CH(CH₃)₂.

Examples of hydroxy (C₁ to C₄) alkoxy residues are —O—CH₂OH, —O—CH₂CH₂OH, —O—CH₂CH₂CH₂OH, —O—CH₂CH(OH)CH₃, —O—CH₂CH₂CH₂CH₂OH.

Examples of (C₁ to C₄) aminoalkyl residues are —CH₂NH₂, —CH₂CH₂NH₂, —CH₂CH₂CH₂NH₂, —CH₂CH(NH₂)CH₃, —CH₂CH₂CH₂CH₂NH₂. An example of aryl groups is the phenyl group, which may also be substituted. Examples of aryl (C₁ to C₄) alkyl groups are the benzyl group and the 2-phenylethyl group.

The agents according to the present specification preferably include as the coloring compound at least one of the following combinations a) to d) of oxidation dye precursors:

-   a) at least one heterocyclic developer selected from pyrazole     derivatives (in particular 1-(2-hydroxyethyl)pyrazole) and     pyrimidine derivatives (in particular     2,4,5,6-tetrahydroxypyrimidone), at least one compound selected from     m-aminophenol or derivatives thereof as coupler, -   b) 4-amino-3-methylphenol, 5-amino-2-methylphenol, -   c) p-toluylenediamine, 4-amino-3-methylphenol,     5-amino-2-methylphenol, -   d) 2-(β-hydroxyethyl)-p-phenylenediamine, 4-amino-3-methylphenol,     5-amino-2-methylphenol.

The agents according to the present specification may also include at least one substantive dye. These are dyes which attach directly to the hair and require no oxidative process to develop the color. Preferred substantive dyes are nitrophenylene diamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

The substantive dyes are each preferably used in an amount from 0.001 to 20 wt. %, relative to the total application preparation. The total amount of substantive dyes is preferably at most 20 wt. %.

Substantive dyes may moreover be divided into anionic, cationic and non-ionic substantive dyes.

Anionic substantive dyes: suitable in particular as anionic substantive dyes are 6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid disodium salt (C.I. 15985; Food Yellow No. 3; FD&C Yellow No. 6), 2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (C.I. 10316; Acid Yellow 1; Food Yellow No. 1), 2-(indane-1,3-dion-2-yl)quinoline-x,x-sulfonic acid (mixture of mono- and disulfonic acid) (C.I. 47005; D&C Yellow No. 10; Food Yellow No. 13; Acid Yellow 3, Yellow 10), 4-((4-amino-3-sulfophenyl)azo)benzenesulfonic acid disodium salt (C.I. 13015, Acid Yellow 9), 5-hydroxy-1-(4-sulfophenyl)-4-[(4-sulfophenyl)azo]pyrazole-3-carboxylic acid trisodium salt (C.I. 19140; Food Yellow No. 4; Acid Yellow 23), 3-[(4-phenylamino)phenyl]azobenzenesulfonic acid sodium salt (C.I. 13065; Ki406; Acid Yellow 36), 9-(2-carboxyphenyl)-6-hydroxy-3H-xanthen-3-one (C.I. 45350; Acid Yellow 73; D&C Yellow No. 8), 5-[(2,4-dinitrophenyl)amino]-2-phenylaminobenzenesulfonic acid sodium salt (C.I. 10385; Acid Orange 3), 4-[(2,4-dihydroxyphenyl)azo]benzenesulfonic acid sodium salt (C.I. 14270; Acid Orange 6), 4-[(2-hydroxynaphth-1-yl)azo]benzenesulfonic acid sodium salt (C.I. 15510; Acid Orange 7), 4-[(2,4-dihydroxy-3-[(2,4-dimethylphenyl)azo]phenyl)azo]benzenesulfonic acid sodium salt (C.I. 20170; Acid Orange 24), 4-hydroxy-3-[(2-methoxyphenyl)azo]-1-naphthalenesulfonic acid sodium salt (C.I. 14710; Acid Red 4), 4-hydroxy-3-[(4-sulfonaphth-1-yl)azo]-1-naphthalenesulfonic acid disodium salt (C.I. 14720; Acid Red No. 14), 6-hydroxy-5-[(4-sulfonaphth-1-yl)azo]-2,4-naphthalenedisulfonic acid trisodium salt (C.I. 16255; Ponceau 4R; Acid Red 18), 3-hydroxy-4-[(4-sulfonaphth-1-yl)azo]-2,7-naphthalenedisulfonic acid trisodium salt (C.I. 16185; Acid Red 27), 8-amino-1-hydroxy-2-(phenylazo)-3,6-naphthalenedisulfonic acid disodium salt (C.I. 17200; Acid Red 33; Red 33), 5-(acetylamino)-4-hydroxy-3-[(2-methylphenyl)azo]-2,7-naphthalenedisulfonic acid disodium salt (C.I. 18065; Acid Red 35), 2-(3-hydroxy-2,4,5,7-tetraiododibenzopyran-6-on-9-yl)benzoic acid disodium salt (C.I. 45430; Acid Red 51), N-[6-(diethylamino)-9-(2,4-disulfophenyl)-3H-xanthen-3-ylidene]-N-ethylethaneammonium hydroxide, internal salt, sodium salt (C.I. 45100; Acid Red 52), 8-[(4-(phenylazo)phenyl)azo]-7-naphthol-1,3-disulfonic acid disodium salt (C.I. 27290; Acid Red 73), 2′,4′,5′,7′-tetrabromo-3′,6′-dihydroxyspiro[isobenzofuran-1(3H),9′-[9H]xanthen]-3-one disodium salt (C.I. 45380; Acid Red 87), 2′,4′,5′,7′-tetrabromo-4,5,6,7-tetrachloro-3′,6′-dihydroxyspiro[isobenzofuran-1(3H),9′[9H]xanthen]-3-one disodium salt (C.I. 45410; Acid Red 92), 3′,6′-dihydroxy-4′,5′-diiodospiro[isobenzofuran-1(3H),9′(9H)-xanthen]-3-one disodium salt (C.I. 45425; Acid Red 95), 2-hydroxy-3-((2-hydroxynaphth-1-yl)azo)-5-nitrobenzenesulfonic acid sodium salt (C.I. 15685; Acid Red 184), 3-hydroxy-4-(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-ylazo)-naphthalene-1-sulfonic acid sodium salt, chromium complex (Acid Red 195), 3-hydroxy-4-[(4-methyl-2-sulfophenyl)azo]-2-naphthalenecarboxylic acid calcium salt (C.I. 15850:1; Pigment Red 57:1), 3-[(2,4-dimethyl-5-sulfophenyl)azo]-4-hydroxy-1-naphthalenesulfonic acid disodium salt (C.I. 14700; Food Red No. 1; Ponceau SX; FD&C Red No. 4), 1,4-bis[(2-sulfo-4-methylphenyl)amino]-9,10-anthraquinone disodium salt (C.I. 61570; Acid Green 25), bis[4-(dimethylamino)phenyl]-(3,7-disulfo-2-hydroxynaphth-1-yl)carbenium internal salt, sodium salt (C.I. 44090; Food Green No. 4; Acid Green 50), bis[4-(diethylamino)phenyl](2,4-disulfophenyl)carbenium internal salt, sodium salt (2:1) (C.I. 42045; Food Blue No. 3; Acid Blue 1), bis[4-(diethylamino)phenyl](5-hydroxy-2,4-disulfophenyl)carbenium internal salt, calcium salt (2:1) (C.I. 42051; Acid Blue 3), N-[4-[(2,4-disulfophenyl)[4-[ethyl(phenylmethyl)amino)phenyl]methylene]-2,5-cyclohexadien-1-ylidene]-N-ethylbenzenemethanaminium hydroxide, internal salt, sodium salt (C.I. 42080; Acid Blue 7), (2-sulfophenyl)di[4-(ethyl((4-sulfophenyl)methyl)amino)phenyl]carbenium disodium salt betaine (C.I. 42090; Acid Blue 9; FD&C Blue No. 1), 1-amino-4-(phenylamino)-9,10-anthraquinone-2-sulfonic acid (C.I. 62055; Acid Blue 25), 1-amino-4-(cyclohexylamino)-9,10-anthraquinone-2-sulfonic acid sodium salt (C.I. 62045; Acid Blue 62), 2-(1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene)-2,3-dihydro-3-oxo-1H-indole-5-sulfonic acid disodium salt (C.I. 73015; Acid Blue 74), 9-(2-carboxyphenyl)-3-[(2-methylphenyl)amino]-6-[(2-methyl-4-sulfophenyl)amino]xanthylium internal salt, sodium salt (C.I. 45190; Acid Violet 9), 1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone sodium salt (C.I. 60730; D&C Violet No. 2; Acid Violet 43), bis[3-nitro-4-[(4-phenylamino)-3-sulfophenylamino]phenyl]-sulfone (C.I. 10410; Acid Brown 13), 5-amino-4-hydroxy-6-[(4-nitrophenyl)azo]-3-(phenylazo)-2,7-naphthalenedisulfonic acid disodium salt (C.I. 20470; Acid Black 1), 3-hydroxy-4-[(2-hydroxynaphth-1-yl)azo]-7-nitro-1-naphthalenesulfonic acid chromium complex (3:2) (C.I. 15711; Acid Black 52), 4-(acetylamino)-5-hydroxy-6-[(7-sulfo-4-[(4-sulfophenyl)azo]naphth-1-yl)azo]-1,7-naphthalenedisulfonic acid tetrasodium salt (C.I. 28440; Food Black No. 1), 3′,3″,5′,5″-tetrabromophenolsulfonephthalein (bromophenol blue), 3,4,5,6,3′,3″,5′,5″-octabromophenolsulfonephthalein (tetrabromophenol blue). Preferred anionic substantive dyes are the compounds known under the international names or trade names tetrabromophenol blue, Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57:1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52.

Cationic substantive dyes: suitable in particular as cationic substantive dyes are 9-(dimethylamino)benzo[a]phenoxazin-7-ium chloride (C.I. 51175; Basic Blue 6), di[4-(diethylamino)phenyl][4-(ethylamino)naphthyl]carbenium chloride (C.I. 42595; Basic Blue 7), di-(4-(dimethylamino)phenyl)-(4-(methylphenylamino)naphthalen-1-yl)carbenium chloride (C.I. 42563; Basic Blue 8), 3,7-di(dimethylamino)phenothiazin-5-ium chloride (C.I. 52015 Basic Blue 9), di[4-(dimethylamino)phenyl][4-(phenylamino)naphthyl]carbenium chloride (C.I. 44045; Basic Blue 26), 2-[(4-(ethyl(2-hydroxyethyl)amino)phenyl)azo]-6-methoxy-3-methylbenzothiazolium methyl sulfate (C.I. 11154; Basic Blue 41), 8-amino-2-bromo-5-hydroxy-4-imino-6-[(3-(trimethylammonio)phenyl)amino]-1(4H)-naphthalenone chloride (C.I. 56059; Basic Blue No. 99), bis[4-(dimethylamino)phenyl]-[4-(methylamino)phenyl]carbenium chloride (C.I. 42535; Basic Violet 1), tri(4-amino-3-methylphenyl)carbenium chloride (C.I. 42520; Basic Violet 2), tri[4-(dimethylamino)phenyl]carbenium chloride (C.I. 42555; Basic Violet 3), 2-[3,6-(diethylamino)dibenzopyranium-9-yl]benzoic acid chloride (C.I. 45170; Basic Violet 10), di(4-aminophenyl)(4-amino-3-methylphenyl)carbenium chloride (C.I. 42510 Basic Violet 14), 1,3-bis[(2,4-diamino-5-methylphenyl)azo]-3-methylbenzene (C.I. 21010; Basic Brown 4), 1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (C.I. 12250; Basic Brown 16), 1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride, 1-[(4-amino-3-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (C.I. 12251; Basic Brown 17), 3-[(4-amino-2,5-dimethoxyphenyl)azo]-N,N,N-trimethylbenzenaminium chloride (C.I. 12605, Basic Orange 69), 3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (C.I. 50240; Basic Red 2), 1,4-dimethyl-5-[(4-(dimethylamino)phenyl)azo]-1,2,4-triazolium chloride (C.I. 11055; Basic Red 22), 2-hydroxy-1-[(2-methoxyphenyl)azo]-7-(trimethylammonio)naphthalene chloride (C.I. 12245; Basic Red 76), di[4-(dimethylamino)phenyl]iminomethane hydrochloride (C.I. 41000; Basic Yellow 2), 2-[2-((2,4-dimethoxyphenyl)amino)ethenyl]-1,3,3-trimethyl-3H-indol-1-ium chloride (C.I. 48055; Basic Yellow 11), 3-methyl-1-phenyl-4-[(3-(trimethylammonio)phenyl)azo]pyrazol-5-one chloride (C.I. 12719; Basic Yellow 57), bis[4-(diethylamino)phenyl]phenylcarbenium hydrogen sulfate (1:1) (C.I. 42040; Basic Green 1), di(4-(dimethylamino)phenyl)phenylmethanol (C.I. 42000; Basic Green 4), 1-(2-morpholiniumpropylamino)-4-hydroxy-9,10-anthraquinone methyl sulfate, 1-[(3-(dimethylpropylaminium)propyl)amino]-4-(methylamino)-9,10-anthraquinone chloride and substantive dyes including a heterocyclic compound having at least one quaternized nitrogen atom.

Preferred cationic substantive dyes are:

-   (a) cationic triphenylmethane dyes, such as for example Basic Blue     7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, -   (b) aromatic systems substituted with a quaternary nitrogen group,     such as for example Basic Yellow 57, Basic Red 76, Basic Blue 99,     Basic Brown 16 and Basic Brown 17, and -   (c) substantive dyes including a heterocyclic compound having at     least one quaternary nitrogen atom, such as for example those     mentioned in EP-A2-998 908, to which reference is explicitly made     here.

Preferred cationic substantive dyes of group (c) are in particular the following compounds:

The compounds of formulae (DZ1), (DZ3) and (DZ5), which are also known under the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are most particularly preferred cationic substantive dyes of group (c).

The cationic substantive dyes which are sold under the ARIANOR® trademark are likewise most particularly preferred cationic substantive dyes according to the present specification.

Non-ionic substantive dyes: non-ionic nitro and quinone dyes and neutral azo dyes in particular are suitable as non-ionic substantive dyes.

Suitable neutral azo dyes are in particular: 1-[di(2-hydroxyethyl)amino]-3-methyl-4-[(4-nitrophenyl)azo]benzene (C.I. 11210, Disperse Red 17), 1-[di(2-hydroxyethyl)amino]-4-[(4-nitrophenyl)azo]benzene (Disperse Black 9), 4-[(4-aminophenyl)azo]-1-[di(2-hydroxyethyl)amino]-3-methylbenzene (HC Yellow 7), 2,6-diamino-3-[(pyridin-3-yl)azo]pyridine, 2-{[4-(acetylamino)phenyl]azo}-4-methylphenol (C.I. 11855; Disperse Yellow 3), 4-[(4-nitrophenyl)azo]aniline (C.I. 11005; Disperse Orange 3).

Preferred non-ionic substantive dyes are the compounds known under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis-(2-hydroxyethyl)amino-2-nitrobenzene, 3-nitro-4-(2-hydroxyethyl)aminophenol, 2-(2-hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-amino-4-(2-hydroxyethyl)amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene, 2-[(4-amino-2-nitrophenyl)amino]benzoic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and salts thereof, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

It is not necessary for the substantive dyes each to be uniform compounds. Instead it is possible for them also to include small amounts of further components arising from the manufacturing processes for the individual dyes, provided that they do not adversely influence the coloring result or need to be excluded for other, for example toxicological, reasons.

Naturally occurring dyes, such as are included for example in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, alder buckthorn bark, sage, logwood, madder root, catechu, lotus and alkanet root, may also be used as substantive dyes.

Indoles and indolines including at least two groups selected from hydroxyl and/or amino groups, preferably as a substituent on the six-membered ring, are preferably used as coloring compounds of the precursors of nature-analogous dyes. These groups may bear further substituents, for example in the form of an etherification or esterification of the hydroxyl group or an alkylation of the amino group. In a further example the coloring agents include at least one indole and/or indoline derivative. Compositions according to the present specification including precursors of nature-analogous dyes are preferably used as air-oxidative coloring agents. In this example said compositions are accordingly not mixed with an additional oxidizing agent.

Derivatives of 5,6-dihydroxyindoline of formula (RN1) are particularly suitable as precursors of nature-analogous hair dyes,

in which, independently of one another,

-   -   R¹ denotes hydrogen, a C₁-C₄ alkyl group or a C₁-C₄ hydroxyalkyl         group,     -   R² denotes hydrogen or a —COOH group, in which the —COOH group         may also be present as a salt with a physiologically acceptable         cation,     -   R³ denotes hydrogen or a C₁-C₄ alkyl group,     -   R⁴ denotes hydrogen, a C₁-C₄ alkyl group or a —CO—R⁶ group, in         which R⁶ denotes a C₁-C₄ alkyl group, and     -   R⁵ denotes one of the groups cited under R⁴,         as well as physiologically acceptable salts of these compounds         with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid.

Within this group, particular emphasis is given to N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and in particular 5,6-dihydroxyindoline.

Derivatives of 5,6-dihydroxyindole of formula (RN2) are moreover outstandingly suitable as precursors of nature-analogous hair dyes,

in which, independently of one another,

-   -   R¹ denotes hydrogen, a C₁-C₄ alkyl group or a C₁-C₄ hydroxyalkyl         group,     -   R² denotes hydrogen or a —COOH group, in which the —COOH group         may also be present as a salt with a physiologically acceptable         cation,     -   R³ denotes hydrogen or a C₁-C₄ alkyl group,     -   R⁴ denotes hydrogen, a C₁-C₄ alkyl group or a —CO—R⁶ group, in         which R⁶ denotes a C₁-C₄ alkyl group, and     -   R⁵ denotes one of the groups cited under R⁴,     -   as well as physiologically acceptable salts of these compounds         with an organic or inorganic acid.

Particularly preferred indole derivatives are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid.

Within this group particular emphasis is given to N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5,6-dihydroxyindole.

The indoline and indole derivatives may be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for example hydrochlorides, sulfates and hydrobromides.

The star polymers used according to the present specification develop their effect particularly in agents for the oxidative coloring of keratin-containing fibers, in particular human hair. It has therefore proved preferable to use an agent according to the present specification for the oxidative coloring of keratin-containing fibers which includes, in a cosmetic carrier,

-   (a) at least one star polymer including a structural fragment acting     as a center and at least three groups radially bound to this center,     wherein these groups     -   (i) each have at least one polyether structural unit comprising         a polyoxyalkylene chain consisting of either ethylene oxide         units or both ethylene oxide and propylene oxide units, wherein         the polyoxyalkylene chain has a maximum proportion of 50 wt. %         of propylene oxide units, relative to the weight of the         polyoxyalkylene chain, and     -   (ii) at least one residue comprising:         -   at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and             R′, independently of one another, denote a (C₁ to C₄) alkyl             group (in particular methyl or ethyl), x denotes 1, 2 or 3;         -   at least one anionic group;         -   at least one quaternized nitrogen atom; or         -   combinations thereof; -   and -   (b) at least one oxidation dye precursor of the developer component     type and optionally additionally at least one coupler component as     the coloring compound, -   and -   (c) at least one oxidizing agent.

The aforementioned preferred features (see above) apply in each case to components (a) and (b) of the agent according to the present specification of this example.

The oxidizing agents within the meaning of the agent differ from atmospheric oxygen and have an oxidizing potential such that they may oxidize an oxidation dye precursor of the developer type. Hydrogen peroxide and/or at least one addition product thereof, in particular with inorganic or organic compounds, such as for example sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone.n H₂O₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide, is preferably suitable as the oxidizing agent.

The oxidizing agent is preferably included in the cosmetic agent in an amount from 1.0 to 10 wt. %, in particular from 3.0 to 10.0 wt. %, relative in each case to the weight of the ready-to-use cosmetic coloring agent.

In a preferred example of the present specification the cosmetic coloring agent according to the present specification is mixed prior to application from a first composition including in a cosmetic carrier at least one color-changing component and a second composition including in a cosmetic carrier at least one oxidizing agent, with the proviso that the first composition and/or the second composition includes at least one star polymer as defined in the second subject matter of the present specification. The first and second compositions are packaged separately from one another each in their own compartment and provided together in the form of a packaging unit (kit). The two components are mixed together shortly before application. The resulting ready-to-use coloring preparation preferably has a pH in the range from 1 to 12, particularly preferably from pH 1 to 10.

The cosmetic coloring agent according to the present specification preferably includes at least one alkalizing agent. The alkalizing agents for use according to the present specification are preferably selected from at least one representative of the group formed from ammonia, basic amino acids, alkali hydroxides, alkanolamines, alkali metal metasilicates, urea, alkali phosphates and alkali hydrogen phosphates. Preferred alkali metal ions are lithium, sodium, potassium, in particular sodium or potassium. The alkalizing agents are moreover preferably different from ammonia.

The basic amino acids which may be used as alkalizing agents according to the present specification are preferably selected from the group formed from L-arginine, D-arginine, D,L-arginine, L-histidine, D-histidine, D,L-histidine, L-lysine, D-lysine, D,L-lysine. Of these, L-arginine, D-arginine, D,L-arginine are particularly preferably used as an alkalizing agent within the meaning of the present specification.

The alkali hydroxides which may be used as the alkalizing agent according to the present specification are preferably selected from the group formed from sodium hydroxide and potassium hydroxide.

The alkanolamines which may be used as the alkalizing agent according to the present specification are preferably selected from primary amines having a C₂-C₆ alkyl parent substance bearing at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group formed from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol. Most particularly preferred alkanolamines according to the present specification are selected from the group including 2-aminoethan-1-ol, 2-amino-2-methylpropan-1-ol and 2-amino-2-methylpropane-1,3-diol.

The alkalizing agent is particularly preferably selected from at least one compound from the group formed from 2-aminoethanol, 2-amino-2-methylpropan-1-ol, 2-amino-2-methylpropane-1,3-diol, potassium hydroxide, L-arginine, D-arginine, D,L-arginine, N-methyl glucamine and urea.

The coloring agents according to the present specification may moreover include further active agents, auxiliary substances and additives, such as for example non-ionic polymers; cationic polymers; zwitterionic and amphoteric polymers; anionic polymers such as for example polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methylvinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert-butyl acrylamide terpolymers; hair-conditioning compounds such as phospholipids; protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, condensation products thereof with fatty acids and quaternized protein hydrolysates; perfume oils, dimethyl isosorbide and cyclodextrins; active agents to improve the fiber structure, in particular mono-, di- and oligosaccharides, such as for example glucose, galactose, fructose, fruit sugars and lactose; cationic surfactants; defoaming agents; anti-dandruff active agents; light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines; active agents such as allantoin, pyrrolidone carboxylic acids and salts thereof as well as bisabolol; vitamins, provitamins and vitamin precursors, in particular those from groups A, B₃, B₅, B₆, C, E, F and H; plant extracts, in particular extracts from green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock, horsetail, whitethorn, lime blossom, almond, aloe vera, pine, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lemon, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, lady's smock, wild thyme, yarrow, thyme, melissa, restharrow, coltsfoot, marshmallow, meristem, ginseng or ginger root; cholesterol; consistency modifiers; fats and waxes; complexing agents; swelling and penetrating substances; opacifiers; pearlescent agents; solid pigments; stabilizing agents for hydrogen peroxide and other oxidizing agents; propellants; antioxidants.

The cosmetic agent according to the present specification may additionally include at least one compound selected from organic amines comprising 2 to 20 carbon atoms, carboxylate complex compounds of tin, alkoxide compounds of tin, carboxylate complex compounds of lead, organoaluminum compounds, metal complexes of organic dicarbonyl compounds and metal complexes of organic dicarboxylic acid esters.

The preferred examples of the first subject matter of the present specification apply with the necessary changes to the second subject matter of the present specification.

The present specification thirdly provides a cosmetic method, comprising

-   (A) applying to keratin-containing fibers a cosmetic agent including     at least one star polymer comprising a structural fragment acting as     a center and at least three groups radially bound to this center,     wherein these groups -   (i) each have at least one polyether structural unit comprising a     polyoxyalkylene chain consisting of either ethylene oxide units or     both ethylene oxide and propylene oxide units, wherein the     polyoxyalkylene chain has a maximum proportion of 50 wt. % of     propylene oxide units, relative to the weight of the polyoxyalkylene     chain, and -   (ii) each have at least one residue comprising:     -   at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′,         independently of one another, denote a (C₁ to C₄) alkyl group         (in particular methyl or ethyl), x denotes 1, 2 or 3;     -   at least one anionic group;     -   at least one quaternized nitrogen atom; or     -   combinations thereof; -   (B) allowing the cosmetic agent to act on keratin-containing fibers     (in particular human hair) that have been synthetically colored with     at least one coloring compound; and (C) after a contact time,     rinsing the cosmetic agent from the keratin-containing fibers. A     preferred example of this method according to the present     specification is a method for coloring keratin-containing fibers in     which an agent of the second subject matter of the present     specification is applied to the fibers and, after a contact time, is     rinsed from the keratin-containing fibers.

The application temperatures may be in a range between 15 and 40 degrees Celsius (° C.). After a contact time of generally 5 to 45 minutes the hair coloring agent is removed by rinsing the hair that is to be colored. There is no need to wash with a shampoo afterwards if a highly surfactant-containing carrier, e.g. a coloring shampoo, was used.

The preferred examples of the first and second subject matter of the present specification apply with the necessary changes to the third subject matter of the present specification.

EXAMPLES

The examples that follow indicate agents that were produced according to the present specification for the treatment of keratinous fibers. Unless otherwise indicated, all values in the following examples are given as weight percent.

The molecular weights given in the examples section are average molecular weights of the starting compounds (polyether polyols) used to produce the prepolymers. The average molecular weight of the polyols may be determined by calculation from the functionality of the compounds or the functionality of the mixture components and the OH number of the compound or the mixture (determined in accordance with Deutsches Institut fur Normung E.V. (DIN) 53240) using end-group analysis. If different compounds are used in place of the polyols as starting compounds, their average molecular weight is important. Thus, for example, the average molecular weight of amines may be determined by end-group analysis with potentiometric titration in accordance with DIN 16945.

Production of Suitable Water-Soluble Polymers Example 1 Three-Arm Triethoxysilyl-Terminated Polyether (PP1)

The polyether polyol that is used is a three-arm random poly(ethylene oxide co-propylene oxide) having an EO/PO ratio of 75/25 and having an average molecular weight of approx. 5000 g/mol, obtained from DOW Chemicals (Voranol® CP 1421). Before the reaction the polyol was heated under vacuum for 1 h at 80° C. with stirring.

(3-Isocyanatopropyl)triethoxysilane (317 mg, 1.0 eq.) was added slowly to the dried polyether polyol (2.04 g, 0.41 mmol). The reaction mixture was stirred for a further 2 days at 100° C. under protective gas until the vibration band for the NCO group disappeared in IR measurement. A product is obtained in which there is a triethoxysilyl group present at each of the free ends of the polymer arms of the star-shaped prepolymer. The product is a colorless, viscous liquid.

Example 2 Six-Arm Triethoxysilyl-Terminated Polyether (PP2)

The polyether polyol that is used is a six-arm random poly(ethylene oxide co-propylene oxide) having an EO/PO ratio of 80/20 and having a molecular weight of 12,000 g/mol, produced by anionic ring-opening polymerization of ethylene oxide and propylene oxide using sorbitol as the initiator. Before the reaction the polyol was heated under vacuum for 1 h at 80° C. with stirring.

A solution of polyether polyol (3 g, 0.25 mmol), triethylenediamine (9 mg, 0.081 mmol) and dibutyl tin dilaurate (9 mg, 0.014 mmol) in 25 ml of anhydrous toluene was prepared, to which a solution of (3-isocyanatopropyl)triethoxysilane (0.6 ml, 2.30 mmol) in 10 ml of anhydrous toluene was added dropwise. The solution was stirred overnight at 50° C. After removing the toluene under vacuum the crude product was repeatedly washed with anhydrous ether. After vacuum drying, a product was obtained having a triethoxysilyl group at each of the free ends of the polymer arms of the star-shaped prepolymer, as a colorless viscous liquid. IR (film, cm⁻¹): 3349 (m, —CO—NH—), 2868 (s, —CH₂—, —CH₃), 1719 (s, —C═O), 1456 (m, —CH₂—, —CH₃), 1107 (s, —C—O—C—), 954 (m, —Si—O—). ¹H-NMR (benzene-d₆, ppm): 1.13 (d, —CH₃ of polymer arms), 1.21 (t, —CH₃ of silane end groups), 3.47 (s, —CH₂ of polymer arms), 3.74 (q, —CH₂ of silane end groups).

Example 3 Mixture of Three-Arm Triethoxysilyl-Terminated Polyether and Eight-Arm Triethoxysilyl-Terminated Polyether (PP3)

The polyether polyol mixture that was used consists of a 3-arm random poly(ethylene oxide co-propylene oxide) (started with glycerol) and an 8-arm polyether polyol (started with cane sugar). The polymer arms are in each case random poly(ethylene oxide co-propylene oxides) having an EO/PO ratio of 75/25. The OH functionality is on average 6.9 (determined by end-group analysis), resulting in an average molecular weight of approx. 12,000 g/mol. A ratio of 78 wt. % 8-arm polyether polyol to 22 wt. % 3-arm polyether polyol is obtained. The polyether polyol mixture was obtained from DOW Chemicals (Voranol® 4053). Before the reaction, the polyether polyol was heated under vacuum for 1 h at 80° C. with stirring.

Dibutyl tin dilaurate (20.9 mg, 0.01%) and (3-isocyanatopropyl)triethoxysilane (30.3 g, 1.0 eq.) were added slowly to the dried polyether polyol (209 g, 16.9 mmol). The reaction mixture was stirred for a further 2 days at 100° C. under protective gas until the vibration band for the NCO group disappeared in IR measurement. A product is obtained in which there is a triethoxysilyl group present at each of the free ends of the polymer arms of the two star-shaped prepolymers. The product is a colorless, viscous liquid.

2.0 Coloring

Relative to the total weight of the mixture, 1.0 wt. % of one of the water-soluble polymers PP1 or PP2 was incorporated into the coloring cream of the commercial product Igora Royal® 6-88 (Schwarzkopf). Immediately before being applied to hair strands (1 gram (g) of standardized “European natural hair 6/0” batch no. 06/2010, N93 from Kerling International, Germany, glued to the hair bundle at one end), the resulting modified coloring cream was mixed with a commercial 6 wt. % hydrogen peroxide-containing developer dispersion Oxigenta® (Schwarzkopf) in the weight ratio 1 to 1 to form a hair coloring agent according to the present specification.

The ready-to-use coloring agent was then applied to a hair strand in the weight ratio 4 g of coloring agent to 1 g of hair, left to act for 30 minutes at 32° C. and then rinsed from the fiber. A total of 4 hair strands were colored in this way. Furthermore, 4 hair strands were colored in accordance with the above procedure using the above commercial product without the addition of said star polymer (as comparative examples, not examples according to the present specification).

The strands were allowed to dry in each case and measured by colorimetry to determine the L,a,b starting values for each strand (Spectraflash 450 device, Colortools software). Eight measuring points were taken for each hair strand, and for each value of the strands colored according to the present specification, sorted in each case by star polymer, and the strands colored not according to the present specification the arithmetic mean was calculated to obtain the L₀,a₀,b₀ values in each case. Exactly the same procedure was used for the following colorimetric measurements.

To determine the wash fastness the hair strands were subjected to a washing procedure that simulates hair washing: an ultrasonic bath was filled with aqueous shampoo solution (2 wt. % of Schauma “7 Kräuter” shampoo). The colored hair strands were immersed in this washing solution and then treated for 15 min with ultrasound (level 5). This treatment corresponds to the cleaning performance of six hair washes. Then the strands were rinsed thoroughly, dried and measured again by colorimetry. The strands were then subjected to a further washing cycle. The wash fastness was assessed from the calculation of the color difference of the strands before washing and after each washing cycle and determined as follows: ΔE−[(L _(i) −L ₀)²+(a _(i) −a ₀)²+(b _(i) −b ₀)²]^(1/2)

-   L_(i), a_(i), b_(i) Values after 6, 12, 18, 24 and 36 hair washes -   L₀, a₀, b₀ Values after 0 hair washes per hair strand

TABLE 1 ΔE after 6, 12, 18, 24 and 30 washes Number of washes 6 12 18 24 30 Commercial product 2.8 3.8 4.6 5.9 6.8 Agent according to the 2.6 3.4 4.1 4.4 4.9 present specification with PP3

While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention, it being understood that various changes may be made in the function and arrangement of the elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims and their legal equivalents. 

The invention claimed is:
 1. A method to improve synthetic colorings of coloring compounds on keratin-containing fibers, comprising applying an active agent comprising at least one coloring compound to color the keratin-containing fibers, and at least one star polymer comprising a structural fragment acting as a center and at least three groups radially bound to this center, wherein these groups: (i) each have at least one polyether structural unit comprising a polyoxyalkylene chain consisting of either ethylene oxide units or both ethylene oxide and propylene oxide units, wherein the polyoxyalkylene chain has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of the polyoxyalkylene chain, and (ii) each have at least one residue comprising: at least one *—Si(OR)_(x)(R)_(3-x) group, in which R and R′, independently of one another, denote a (C₁ to C₄) alkyl group, x denotes 1, 2 or 3; at least one anionic group; at least one quaternized nitrogen atom; or combinations thereof.
 2. A cosmetic agent for coloring keratin-containing fibers, comprising, in a cosmetic carrier: (a) at least one star polymer comprising a structural fragment acting as a center, and at least three groups radially bound to this center, wherein these groups: (i) each have at least one polyether structural unit comprising a polyoxyalkylene chain consisting of either ethylene oxide units or both ethylene oxide and propylene oxide units, wherein the polyoxyalkylene chain has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of the polyoxyalkylene chain, and (ii) each have at least one residue comprising: at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′, independently of one another, denote a (C₁ to C₄) alkyl group, x denotes 1, 2 or 3; at least one anionic group; at least one quaternized nitrogen atom; or combinations thereof, and (b) at least one coloring compound to color the keratin-containing fibers, in which the at least one coloring compound comprises at least one of: (i) an oxidative dye precursor of a developer component type; (ii) a substantive dye; and (iii) a precursor of a nature-analogous dye; in which the change in color of the keratin fibers that results from the treatment of the keratin fibers with the agent persists through the first shampoo of the keratin fibers following treatment with the agent.
 3. The cosmetic agent of claim 2, wherein the at least one star polymer comprises a compound of general formula (PE-1): [Q

K′-A-K-T)_(n)  (PE-1) in which: A denotes a polyoxyalkylene chain consisting of either ethylene oxide units or both ethylene oxide and propylene oxide units, wherein the polyoxyalkylene chain has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of A, K and K′ independently of one another, denote a connectivity selected from a covalent bond or a molecular fragment having two free valences, T denotes a structural fragment comprising at least one *—Si(OR)_(x)(R)_(3-x) group, in which R and R′, independently of one another, denote a (C₁ to C₄) alkyl group, x denotes 1, 2 or 3; at least one anionic group; at least one quaternized nitrogen atom; or combinations thereof, Q denotes an organic structural fragment acting as a center and derived from linear, branched, cyclic or heterocyclic hydrocarbons, all of which may each be saturated, unsaturated or aromatic, n denotes an integer from 3 to
 64. 4. The cosmetic agent of claim 2, wherein the at least one star polymer comprises a structural fragment acting as the center that is a solid particle which is modified at the surface with at least three *—K′-A-K-T residues, in which: A denotes a polyoxyalkylene chain consisting of either ethylene oxide units or both ethylene oxide and propylene oxide units, wherein the polyoxyalkylene chain has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of A, K and K′ independently of one another, denote a connectivity selected from a covalent bond or from a molecular fragment having two free valences, T denotes a structural fragment comprising at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′, independently of one another, denote a (C₁ to C₄) alkyl group, x denotes 1, 2 or 3; at least one anionic group; at least one quaternized nitrogen atom; or combinations thereof.
 5. The cosmetic agent of claim 3, wherein A denotes a structural fragment of formula (A1) *-(OCH₂CH₂)_(n)—(OCH₂CH(CH₃))_(m)—*  (A1) in which: n denotes an integer from 1 to 500, m denotes an integer from 0 to 500, and n and m are selected such that the structural fragment of formula (A1) has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of the structural fragment (A1).
 6. The cosmetic agent of claim 4, wherein A denotes a structural fragment of formula (A1) *-(OCH₂CH₂)_(n)—(OCH₂CH(CH₃))_(m)—*  (A1) in which: n denotes an integer from 1 to 500, m denotes an integer from 0 to 500, and n and m are selected such that the structural fragment of formula (A1) has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of the structural fragment (A1).
 7. The cosmetic agent of claim 3, wherein the residues K and K′, independently of one another, denote a covalent bond, an oxy group, an imino group, a (C₁ to C₆) alkylene group or at least one of the following connectivities (K1) to (K10)

in which R and R″ independently of one another, denote methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl or phenylene, R′ denotes a hydrogen atom or a (C₁ to C₄) alkyl group, R′″ independently of one another, denotes a (C₁ to C₄) alkyl group or an aryl group.
 8. The cosmetic agent of claim 4, wherein the residues K and K′, independently of one another, denote a covalent bond, an oxy group, an imino group, a (C₁ to C₆) alkylene group or at least one of the following connectivities (K1) to (K10)

in which R and R″ independently of one another, denote methylene, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl or phenylene, R′ denotes a hydrogen atom or a (C₁ to C₄) alkyl group, R′″ independently of one another, denotes a (C₁ to C₄) alkyl group or an aryl group.
 9. The cosmetic agent of claim 2, wherein said at least one star polymer is included in an amount of from 0.01 to 10.0 weight percent (wt. %), relative to the total weight of the agent.
 10. The cosmetic agent of claim 2, wherein said at least one star polymer is included in an amount of from 0.1 to 2.0 wt. %, relative to the total weight of the agent.
 11. The cosmetic agent of claim 2, wherein said at least one star polymer is included in an amount of from 0.2 to 1.0 wt. %, relative to the total weight of the agent.
 12. The cosmetic agent of claim 2, wherein the cosmetic agent additionally comprises at least one compound selected from organic amines comprising 2 to 20 carbon atoms, carboxylate complex compounds of tin, alkoxide compounds of tin, carboxylate complex compounds of lead, organoaluminum compounds, metal complexes of dicarbonyl compounds and metal complexes of organic dicarboxylic acid esters.
 13. The cosmetic agent of claim 2, further comprising at least one oxidizing agent.
 14. The cosmetic agent of claim 13, wherein the oxidizing agent is hydrogen peroxide or at least one addition product thereof.
 15. The cosmetic agent of claim 2, wherein the coloring compound comprises at least one oxidation dye precursor of the developer component type.
 16. The cosmetic agent of claim 15, further comprising at least one coupler component.
 17. A cosmetic method, comprising: (A) applying to keratin-containing fibers a cosmetic agent comprising at least one coloring compound to color the keratin-containing fibers, and at least one star polymer comprising a structural fragment acting as a center and at least three groups radially bound to this center, wherein these groups: (i) each have at least one polyether structural unit comprising a polyoxyalkylene chain consisting of either ethylene oxide units or both ethylene oxide and propylene oxide units, wherein the polyoxyalkylene chain has a maximum proportion of 50 wt. % of propylene oxide units, relative to the weight of the polyoxyalkylene chain, and (ii) each have at least one residue comprising: at least one *—Si(OR)_(x)(R′)_(3-x) group, in which R and R′, independently of one another, denote a (C₁ to C₄) alkyl group, x denotes 1, 2 or 3; at least one anionic group; at least one quaternized nitrogen atom; or combinations thereof; (B) allowing the cosmetic agent to act on keratin-containing fibers; and (C) after a contact time, rinsing the cosmetic agent from the keratin-containing fibers.
 18. The method of claim 1, wherein the at least one coloring compound comprises a compound selected from the group consisting of: (A) at least one substantive dye; and (B) at least one precursor of nature-analogous dyes.
 19. The method of claim 1, wherein the at least one coloring compound comprises an oxidative dye of the developer component type.
 20. The cosmetic agent of claim 2, wherein the at least one coloring compound comprises a compound selected from the group consisting of: (A) at least one substantive dye; and (B) at least one precursor of nature-analogous dyes. 